Glycosaminoglycan and cationic polymer combinations

ABSTRACT

Combinations of glycosaminoglycan and certain cationic polymers provide modified glycosaminoglycan properties and can provide substantivity to keratinous material, compatibility, stability, humectancy, rheology and other properties useful in personal care or medical applications.

BACKGROUND OF THE INVENTION

1. Field of the Invention

This invention relates to polymeric combinations and more particularlyto combinations of glycosaminoglycan and cationic polymer and toprocesses for managing keratinous material and modifyingglycosaminoglycan properties using such combinations.

2. Description of Background Information

Glycosaminoglycans provide significant utility in biological systems.Glycosaminoqlycans can provide high viscosity and elasticity when inaqueous solution by absorbing large volumes of water. In biologicalsystems these properties enable glycosaminoglycans to stabilize andsupport fibrous components and cellular structures and contribute towater maintenance and salt balance in tissues. Variousglycosaminoglycans have been utilized in medical and personal careapplications. For example, one such glycosaminoglycan, hyaluronan, has ahigh capacity to hold water and provide a gel-like substance whichexhibits unique properties characteristic of a true liquid by beingcapable of dilution and exhibiting viscous flow as well as elastic andpseudoplastic properties. As used herein, the terms "glycosaminoglycan"and "hyaluronan" include both the free acid and corresponding saltforms, consistent with accepted nomenclature as described by E. A.Balazs et al., Biochemical Journal Letters, Volume 235, p. 903 (1986).Detailed descriptions of the structure, properties and uses ofhyaluronan are presented in the literature articles: Balazs, E.A. andBand, P., "Hyaluronic Acid: Its Structure and Use", Cosmetics &Toiletries, June 1984, Volume 99, Pages 65-81; and Band, P., "EffectiveUse of Hyaluronic Acid", Drug and Cosmetic Industry, October 1985,Volume 137, Pages 54-56.

The use of qlycosaminoglycans, such as hyaluronan, and the ability totake full advantage of the unique properties of such materials incertain medical and personal care applications is, however, limited by ageneral lack of substantivity of such material to keratinous substrates,such as hair, skin or like materials. Glycosaminoglycans, are anionicpolymers, which disassociate in aqueous solution, providing a negativecharge inhibiting its deposition and retention on similarly negativelycharged, keratinous materials.

Various cationic polymers, such as quaternary nitrogen containingcellulose ethers, including those described in U.S. Pat. No. 3,472,840(Stone, et al.), are substantive to keratinous materials. Such polymersare readily deposited and retained on keratinous materials such that theproperties of such polymers have increased effect on the keratin inproviding, for example, improved conditioning, manageability or otherdesirable properties.

Combinations of anionic and cationic polymers in general are known anddescribed in personal care applications. U.S. Pat. No. 4,240,450(Grollier, et al.) and various references cited therein, describecompositions containing anionic polymer, cationic polymer and surfactantin a solvent medium, for use in treating keratin materials. Grollier, etal. disclose that various anionic polymers may be anchored to keratinmaterial when used in combination with cationic polymers. Variousproperties and applications of anionic and cationic polymer combinationsare summarized in a review by Petrak, K., entitled "PolyelectrolyteComplexes in Biomedical Applications", in the Journal of Bioactive andCompatible Polymers, Vol. 1, April, 1986, pages 202-219. Hair carecompositions containing the ionic reaction product of cationic andanionic polymers are described in U.S. Pat. No. 4,299,817, (Hannan III,et al.). Water soluble and water insoluble gels provided by interpolymerreactions of selective anionic and cationic polymers, useful in cosmeticcompositions are described in U.S. Pat. No. 4,501,834 (Su).Polyelectrolyte complexes of hyaluronan and glycol chitosan, a cationicpolymer, are described by A. Nakajima et al. in an article entitled"Complex Formation Between Oppositely Charged Polysaccharides" in theJournal of Colloid and Interface Science, Vol. 55, No. 1, April, 1976,pages 126-132.

Combinations of anionic and cationic polymers, however, areunpredictable in their ability to provide substantivity of the anionicpolymer to keratinous material, as well as in their ability to provide awide variety of properties either required or desirable for variousmedical or personal care applications. Compositions containing bothanionic and cationic polymers, due in part to their contrastingelectrical charge and resulting characteristics, are generally limitedin their ability to provide compatible, stable solutions exhibitinguseful rheological properties and/or substantivity, particularly whencombined with typical additives used in personal care or medicalproducts.

It would be desirable if compositions and processes could be providedwhich contain glycosaminoglycan and cationic polymer which aresubstantive to keratinous materials to maximize the benefits provided byboth polymers. Such compositions and processes should have sufficientcompatibility and stability to be useful in various solvent systems, andpreferably provide rheological properties suitable for a wide range ofend uses.

SUMMARY OF THE INVENTION

This invention pertains to combinations comprising cationic polymer andglycosaminoglycan as well as to particular embodiments of suchcombinations. Processes for modifying glycosaminoglycan properties andfor managing keratinous material by applying an effective managingamount of such combinations to keratinous substrate are also provided.

DETAILED DESCRIPTION OF THE INVENTION

This invention pertains to combinations of, and processes using,glycosaminoglycan and cationic polymers which provide uniquemodification of the properties exhibited by the glycosaminoglycan. Inparticular, the properties provided by the glycosaminoglycan areincreased or enhanced by combination with the cationic polymer. Inaddition, the glycosaminoglycan can be made substantive to keratinousmaterial through the presence of the cationic polymer. Compositions andprocesses are also described which provide such combinations withcompatibility, stability and exhibit rheological properties for utilityin a wide variety of applications.

Cationic polymer and glycosaminoglycan combinations are provided whichform uniform viscoelastic matrixes. These surface matrixes act asreenforcement when applied to keratinous substrate by generating highlyflexible and strong structural films. This results in well hydratedsubstrate protected from environmental attack by the uniform surfacecovering, which can be retained even after water immersion. When appliedto the skin, the combination has excellent rub in and afterfeelproperties. The substantivity of the combination extends the time theglycosaminoglycan remains in contact with the keratinous substrate fordelivering the benefits of the glycosaminoglycan to the substrate.Increased humectancy, i.e. moisturization, is provided using a hydratedmatrix of cationic polymer and glycosaminoglycan taking advantage ofglycosaminoglycan properties for holding water, such as has beendemonstrated in intercellular matrix of dermal connective tissue.

Glycosaminoglycans are well known, naturally occurring, polysaccharidescontaining disaccharide repeating units of hexosamine and hexose orhexuronic acid, and may contain sulfate groups.

The size, type or form of glycosaminoglycan provided is not narrowlycritical to this invention. The molecular weight of theglycosaminoglycan is not critical and may range from about 5,000 toabout 20,000,000, preferably from about 100,000 to about 12,000,000, andmost preferably from about 1,000,000 to about 10,000,000.Glycosaminoglycan may be provided in free acid or salt form. Theglycosaminoglycate may be associated with any suitable cation,including, but not limited to: alkali metals, such as sodium andpotassium; alkaline earth metals; nitrogen containing cations, such asammonium, substituted ammonium and quaternized derivatives thereof; andother suitable cations. Preferred salts of glycosaminoglycans andderivatives thereof include alkali metal or alkaline earth metalglycosaminoglycates. The glycosaminoglycan may be provided: in pureform; as a mixture of glycosaminoglycan with proteins and naturallyoccurring substances derived by the production of glycosaminoglycan fromnatural material; or as a chemically modified, glycosaminoglycanderivative. Mixtures of such glycosaminoglycans may also be provided.

Representative glycosaminoglycans include, but are not limited to:hyaluronan or derivatives thereof such as hylan; heparin; heparan;chondroitin; keratan; dermatan; and sulfates of such materials. Aparticularly preferred glycosaminoglycan is hyaluronan, and derivativesthereof, which contain repeating disaccharide structure of D-glucuronicacid and 2 -acetamido-2-desoxy-D-glucose joined by alternating β1→3glucuronidic and β1→4 glucosaminidic bonds. Representative hyaluronanand derivatives thereof which may be provided include, but are notlimited to: BIOMATRIX ® hyaluronan provided by Biomatrix, Inc., such asdescribed in U.S. Pat. No. 4,303,676 (Balazs) which is incorporatedherein by reference, HYLADERM® hylan provided by Biomatrix, Inc., suchas described in U.K. Published Patent Application No. 2,172,295A(Balazs, et al.) which is incorporated herein by reference; andsubstantially pure hyaluronan such as described in U.S. Pat. No.4,141,973 (Balazs) which is incorporated herein by reference.

In the broadest sense, any cationic polymer may be used which, whencombined with glycosaminoglycan, provides a modification in theproperties of the glycosaminoglycan, such as improved rheology,increased substantivity and preferably other desired properties. Suchcationic polymers may be selected from within the class of cationicpolymers which provide substantivity to keratinous material. Suchcationic polymers may be either synthetic or naturally occurringmaterials. The synthetic polymers may be produced by addition orcondensation polymerizations or may derived by chemical modification ofnaturally occurring polymers. The particular polymeric structure is notcritical so long as the cationic polymer provides the requisitemodification of glycosaminoglycan properties, and preferably additionaldesirable properties, as hereinafter discussed.

Representative cationic polymers which may be provided include, but arenot limited to: polysaccharide, condensation polymer, polyalkylenimine,and homo- or copolymer of ethylenically unsaturated compounds; whichpolymer contains cationic substitution, such as by containing cationizednitrogen, phosphorus or sulfur groups. Representative polysaccharidesinclude, but are not limited to: the starch and cellulose families;pectin; chitin; chitosan; guar; and the like. Representativepolyalkylenimines include, but are not limited to; poly N-acylalkylenimines, and hydrolyzed derivatives thereof. Representative homo-or copolymers of ethylenically unsaturated compounds include, but arenot limited to: poly(meth)acrylamides, polyvinyl pyrrolidones,poly(meth)acrylates, diallyl dialkyl ammonium halides, as well as graftsor copolymers of such materials.

Preferred cationic polymers include, but are not limited to, watersoluble polymers which may be selected from the following: quaternarynitrogen-containing cellulose ethers such as UCARE® Polymers JR-125,JR-400, JR-30M, LR-400, LR-30M and SR-10 provided by Union CarbideCorp., and as described in U.S. Pat. No. 3,472,840 (Stone, et al.) whichis incorporated herein by reference; hydrophobe modified, quaternarynitrogen-containing polysaccharides, such as QUATRISOFT™ Polymersprovided by Union Carbide Corp., and as described European PublishedPatent Application No. 189,935 which is incorporated herein byreference; graft copolymers of cellulose ethers and dialkyl diallylammonium halide, such as CELQUAT® Polymers provided by National Starch;quaternarized nitrogen-substituted galactomannan, such as JAGUAR®Polymers provided by Celanese; homo- and copolymers of dialkyl diallylammonium halide, such as MERQUAT® Polymers provided by Calgon;copolymers of vinyl pyrrolidone and quaternized dialkylaminoalkylmethacrylate such as GAFQUAT® Polymers provided by GAF Corp.; copolymersof acrylamide and quaternized, dialkyl amino dialkyl methacrylate, suchas RETEN® Polymers provided by Hercules, Inc.; and other cationicpolymers including polymers identified as polyquaternium compounds bythe Cosmetics, Toiletries and Fragrance Association (CTFA).

Particularly preferred cationic polymers include certain water soluble,quaternary nitrogen containing polysaccharides represented by theoverall structural formula: ##STR1##

In Formula II, R_(sacch) is the residue of a polysaccharide repeat unit.The polysaccharide repeat unit may contain more than three "R"substituents for those polysaccharides which contain more than threereactive hydroxyl groups per repeat unit. R_(sacch) is preferably theresidue of an anhydroglucose repeat unit, particularly from cellulose.

The parameter Q in Formula II varies depending upon the particularpolysaccharide being utilized. For example, Q is --O-- when theparticular polysaccharide comprises anhydroglucose repeat units such asin starch, cellulose or the like. Similarly, Q is: ##STR2## wherein R₄is ##STR3## in chitin and wherein R₄ is a mixture of hydrogen and groupsin chitosan. Q is preferably --O--, i.e. an oxygen atom.

The number of polysaccharide repeat units, defined by z in Formula II,is usually from about 50 to about 20,000, preferably from about 100 toabout 6,000; and most preferably from about 250 to about 4,000. Thecorresponding molecular weights of the cationic polysaccharide willusually range from several thousand up to several million.

The R₁, R₂ and R₃ substituents in Formula II are either hydrogen, whenrepresenting unreacted hydroxyl groups of the polysaccharide, orsubstituents provided by etherification, quaternization and/or otherderivitization. Each R₁, R₂ and R₃ is individually represented by thesubstituent structural formula: ##STR4##

In Formula III, A is an anion, including mixtures of anions. Exemplaryanions include inorganic anions such as chloride, bromide, iodide,sulfate, methylsulfate, sulfonate, nitrate, phosphate, and the like; andorganic anions such as acetate, and the like. Monovalent anions arepreferred, particularly halides, and especially chloride. The anions aretypically provided as the residue of the quaternary ammonium salts usedas quaternizing agents, or by other known techniques.

The alkylene substituent defined by a in Formula III, contains from 1 toabout 3 carbon atoms such that a is an integer having a value of from 1to about 3.

The extent of etherification due to oxyalkylene substituents, as definedby m and p in Formula III, generally ranges from 0 to about 6oxyalkylene groups each, i.e. m is an integer of from 0 to about 6 and pis an integer of from 0 to about 6. The additional extent ofetherification, as defined by q in Formula II, depends upon the absenceor presence of the alkylene group, i.e. C_(a) H_(2a), such that q is 0or 1, preferably 0.

The total extent of etherification, as measured in terms of molarsubstitution, i.e., MS, is usually greater than 0, generally from about1.2 to about 4.5, and preferably from about 1.8 to about 3.6.

The number of quaternary nitrogen atoms per substituent, defined by n inFormula III, is greater than or equal to 0, i.e. n is an integer greaterthan or equal to 0. The extent of quaternization throughout thepolysaccharide, characterized as the degree of cationic substitution,i.e. CS, provides an average value per repeat unit which is greater than0, and in some embodiments is generally less than 1 and preferably fromabout 0.01 to about 0.6.

Each R₅ and R₇ in Formula III, defining the oxyalkylene substituent, isindividually an ethylene (providing oxyethylene), a propylene (providingoxypropylene) or a hydroxypropylene (providing hydroxy substitutedoxypropylene) unit. R₅ and R₇ are preferably ethylene orhydroxypropylene, and most preferably ethylene.

The segment connecting the quaternary nitrogen to the polysaccharidemolecule, defined as R₆ in Formula III, is a di or a trivalent, cyclic,branched or straight chain, saturated or unsaturated hydrocarbon havingfrom 2 to about 6 carbon atoms, provided that there are at least 2carbon atoms between the nitrogen atom and any oxyqen atom, such as inthe ether substituent or polysaccharide residue. R₆ can be ethylene, aC₃ hydrocarbon group, --CH₂ CH=CHCH₂ --, or when combined with R₉, R₁₀or R₁₁ can be cycloalkyl suc as ##STR5## Most preferably R₆ is ##STR6##

R₈ in Formula III is hydrogen, hydroxyl, a hydrophobic group R_(h),alkyl, carboxyl, alkali metal or amine carboxylate, or other terminalgroup provided that when q is 0 then R₈ is hydrogen or alkyl. R₈ ispreferably hydrogen or alkyl. When R₈ is hydrogen and m, n, p and q areall 0 the substituent structural formula provides an unsubstitutedpolysaccharide hydroxyl group.

The nitrogen substituents, defined by R₉, R₁₀ and R₁₁ in Formula II, areeach individually a hydrophobic group R_(h), alkyl, aryl, aralkyl,alkaryl, cycloalkyl, alkoxyalkyl, alkoxyaryl or together with R₆ form anitrogen-containing heterocyclic ring. If an alkoxyalkyl or alkoxyarylsubstituent is provided, at least two carbon atoms separate thesubstituent oxygen atom from the nitrogen atom. Nitrogen substituentsinclude: lower alkyls having from 1 to about 3 carbon atoms, such asmethyl, or ethyl; aryls such as phenyl; aralkyls such as benzyl; or,together with R₆, dialkyl substituted cycloalkyl such as N,N-dimethylpyrrolidyl; and the like. Preferred nitrogen substituents of each repeatunit are methyl, a hydrophobic group, or together with R₆ provide apyrrolidyl, or are a mixture of such groups.

When present, the hydrophobic group, defined by R_(h), contains a longchain alkyl group having at least 8 carbon atoms, preferably from about10 to about 24 carbon atoms, and most preferably from about 10 to about18 carbon atoms. The hydrophobic group is attached directly to thequaternary nitrogen when present as R₉, R₁₀ or R₁₁ ; to the ethersubstituent R₈ ; and/or directly to the polysaccharide residue as R₈when m, n, p and q are all zero. The hydrophobic group may be providedat any or all of these locations, in the same or different repeat unitswithin the polysaccharide molecule. The hydrophobic group may alsocontain a connecting segment between the alkyl group and the nitrogen oroxygen atom to which the group is connected, depending upon thealkylating agent used to connect the alkyl group to the polysaccharide.The hydrophobic group is preferably a long chain alkyl group bondeddirectly to a nitrogen or oxygen atom, and most preferably to thequaternary nitrogen.

The valence of anion A, defined as v in Formula III, is an integer,preferably 1.

The absence or presence of the ether oxygen in the quaternary nitrogensubstituent is defined by y in Formula III, i.e., y is 0 or 1,respectively, provided that in the absence of further ethersubstitution, i.e. when n is greater than 0 and y is 0, then p and q are0 and R₈ is hydrogen. Preferably y is 1.

Illustrative of some of the numerous possible substituents for anindividual polysaccharide repeat unit include the following: ##STR7##wherein R is lower alkyl, and m and n are as defined previously.

In a preferred embodiment, the cationic polymer is a cellulose etherrepresented by the overall structural formula: ##STR8## wherein:

R_(cell) is the residue of an anhydroglucose repeat unit;

and z, R₁, R₂ and R₃ are as defined previously except for the furtherprovisos that:

(1) the extent of hydrophobic group substitution, HS, defined by theaverage moles of said hydrophobic groups per mole of polysacchariderepeat unit, is greater than 0; or

(2) any one of R₉, R₁₀ or R₁₁ taken together with R₆ forms aheterocyclic ring and the average value of n per polysaccharide repeatunit, is greater than 0.

The specific amount of glycosaminoglycan provided is not narrowlycritical. Generally, an effective managing amount, which is defined asthat amount of glycosaminoglycan sufficient to provide effective orimproved keratin treatment utility to the combination, is provided.Typically, the amount of glycosaminoglycan is at least about 0.0001 wt.%, preferably from about 0.0005 wt. % to about 2 wt. %, and mostpreferably from about 0.001 wt. % to about 1 wt. % of the totalcomposition.

The specific amount of cationic polymer provided is not critical, solong as an effective amount sufficient to modify glycosaminoglycanperformance, as hereinafter discussed, is provided. Typically, theamount of cationic polymer is at least about 0.0005 wt. % preferablyfrom about 0.0025 wt. % to about 20 wt. %, and most preferably fromabout 0.005 wt. % to about 10 wt. % of the total composition.

In the broadest sense, the relative proportion of cationic polymer toglycosaminoglycan is not narrowly critical except that an effectiveamount of cationic polymer is provided which is sufficient to modifyglycosaminoglycan properties. The relative weight ratio of cationicpolymer to glycosaminoglycan will generally range from about 0.01:1 toabout 200:1, preferably from about 2:1 to about 100:1, and mostpreferably from about 10:1 to about 50:1.

Variations in the relative weight ratio of cationic polymer toglycosaminoglycan can provide properties including improvedglycosaminoglycan rheology and substantivity, as well as compatibility,enhanced feel and extended stability. An enhanced degree ofglycosaminoglycan substantivity can be provided when applied tokeratinous substrate, such as hair or skin. Enhanced substantivity toskin may be provided at relative weight ratios of cationic polymer toglycosaminoglycan of greater than about 5:1, and preferably from about35:1 to about 75:1. Enhanced glycosaminoglycan substantivity to hair canbe provided using relative weight ratios of cationic polymer toglycosaminoglycan of from about 5:1 to about 25:1. The relative weightratios providing enhanced substantivity can vary depending upon the typeand amount of cationic polymer and glycosaminoglycan, as well as thepresence and amount of additional ingredients, such as surfactants orother personal care compounds.

The glycosaminoglycan and cationic polymer combination provides a uniqueand surprising modification in the properties of the glycosaminoglycan.In the broadest sense, this modification in glycosaminoglycan propertiesis characterized by an increase or enhancement in the propertiesexhibited by the glycosaminoglycan which may include, but is not limitedto, its rheology or substantivity to keratinous material.

Modification of glycosaminoglycan performance can be determined throughanalysis of the properties provided by the glycosaminoglycan throughcomparison with and without the presence of the cationic polymer. Inparticular, glycosaminoglycan properties, such as providing compositionswith superior feel characteristics, are provided having substantiallyreduced concentrations of glycosaminoglycan when in combination withcationic polymer of this invention.

The glycosaminoglycan and cationic polymer combination can also providesubstantivity of the glycosaminoglycan to keratinous material. Thesubstantivity of this invention does not simply pertain to theproperties of the cationic polymer but extends to the glycosaminoglycanin that the composition provides substantivity of glycosaminoglycan tokeratinous material.

Substantivity of the glycosaminoglycan and cationic polymer combinationis characterized by an increase in the deposition or retention, or both,of the glycosaminoglycan on keratinous material due to the presence ofthe cationic polymer, as compared to deposition or retention of anequivalent amount and kind of glycosaminoglycan on keratinous materialin the absence of the cationic polymer.

Substantivity can be measured through analysis of radiolabelledglycosaminoglycan. In particular, tritiated glycosaminoglycan containing6-³ H-D-glucosamine units may be provided, using well establishedtechniques such as in vitro tissue culture methodology. When suchradiolabelled glycosaminoglycan is applied to keratinous substrates thedegree of substantivity can be determined by measuring the amount ofglycosaminoglycan deposited or retained on the substrate throughdetecting the amount of radioactivity on the treated keratin.Substantivity can also be determined using electrokinetic streamingpotential analysis, such as described in an article by Somasundaran etal., J. Colloid Interface Science, Vol. 45, 591 (1973). In particular,from measurement of the electrokinetic potential of hair samples treatedwith a combination of cationic polymer and glycosaminoglycan using alarge excess of cationic polymer, it can be inferred that substantivityof glycosaminoglycan in a bound complex with the cationic polymer isachieved. Substantivity is determined through detection of adsorptionand retention of the cationic polymer through electrokinetic potentialanalysis of such a combination. In addition, a change in electrokineticstreaming potential caused by application of glycosaminoglycan after aninitial application of cationic polymers also shows substantivity of theglycosaminoglycan.

The glycosaminoglycan and cationic polymer combination can also possessdesirable compatibility, stability and/or rheology.

Compatibility, as defined in this invention, is characterized byglycosaminoglycan/cationic polymer combinations which provide ahomogeneous, single phase composition, such as an aqueous solution inwhich no precipitation occurs over at least a 24 hour period aftercombining the glycosaminoglycan and cationic polymer.

Compatibility can be determined through optical or viscosity analysis.In particular, the absorbance of compositions of glycosaminoglycan andcationic polymer can be measured, such as through visible absorbancemeasurements generally taken at 540 nanometers, initially and over 24hours. Compositions which do not possess compatibility form aprecipitate or provide decreasing absorbance of the remaining solublecomposition within 24 hours. Compatibility can also be determined bymeasuring the viscosity of compositions of glycosaminoglycan andcationic polymer or dilutions thereof. Incompatible compositions providesolutions where the remaining soluble composition exhibits a reductionin viscosity within 24 hours.

Stability, as defined in this invention, is characterized byglycosaminoglycan and cationic polymer combinations which providecompositions possessing minimal destabilization over time or afterfreezing and thawing, such as through avoiding the formation ofprecipitates or coacervates, loss of homogeneity or a change inrheological properties.

Storage stability can be determined by analyzing glycosaminoglycan andcationic polymer combinations under controlled conditions, such as forseveral, such as four, months at various temperatures, such as 4° C.,through visual observation of homogeneity, precipitate or coacervate andby optical, viscosity or other rheological measurement, usingestablished procedures. Long term stability is demonstrated for samplesexhibiting little or no change in properties. Freeze thaw stability canbe determined using similar analyses of such combinations subjected torepeated freezing and thawing cycles.

Rheology, as defined in this invention, is characterized by viscosity,elasticity or other rheological properties of glycosaminoglycan andcationic polymer compositions, such as through analysis of compositionsof glycosaminoglycan and cationic polymer with respect to viscosity as afunction of shear rate and modulus of elasticity as a function offrequency of oscillation, using established procedures. Suchcompositions exhibit synergistic increases in shear viscosity andmodulus of elasticity when compared with the sum of such values providedby the same type and amount of cationic polymer and glycosaminoglycanindividually. The degree of enhanced rheology will generally varydepending upon the type and amount of cationic polymer andglycosaminoglycan, the relative weight ratio thereof, as well as thepresence and amount of other compounds.

The presence and degree of compatibility, stability, and rheologyprovided by the glycosaminoglycan and cationic polymer combination willgenerally vary depending upon the particular type and form ofglycosaminoglycan and cationic polymer, and relative proportions of thetwo components, and will be influenced by the presence and amount ofother material effecting the interaction between the glycosaminoglycanand cationic polymer.

The glycosaminoglycan and cationic polymer combination of this inventionprovides utility in kericare applications. The term kericare as used inthis invention describes the treatment or care of keratinous material,such as hair, skin, nails or other like material, and encompasses bothmedical and personal care applications.

Illustrative medical uses of this invention include, but are not limitedto, the following: viscosurgery; coatings to improve the bicompatabilityof various materials; wound dressings; various pharmaceuticalpreparations; drug delivery; and other medical applications.

Illustrative personal care uses of this invention include, but are notlimited to, the following: skin creams including cleansing, night,massage, moisturizing, vanishing, foundation, hand, hand-and-body,all-purpose creams and other known skin creams; astringents and skintonics, including compositions for irritated, inflamed, allergic,hypersensitive or sensitized skin; protective creams and hand cleansers;bath preparations including foam baths, bath salts, bath oils, afterbath products, and other known bath preparations; baby skin and hairproducts; adolescent skin products, such as for oily skin or acne, andother known adolescent skin products; antiperspirants and deodorants;depilatories; shaving preparations including wet shaving creams, sticks,foams, dry shaving lotions, powder, after shave lotions, foams,aerosols, gels, creams, balms and powders, and other known shavingpreparations; foot preparations including foot powders, sprays, creams,corn, callus and chilblain and athlete's foot preparations and otherknown foot preparations; insect repellants; sunscreen, suntan andanti-sunburn preparations; skin lighteners or bleaches; face packs ormasks including wax-, rubber-, vinyl-, hydrocolloid- or earth-basedsystems, anti-wrinkle preparations and other known face packs or masks;perfumes; face powders and make-up; colored make up preparationsincluding lipstick, lip salves, rouge, eye make-up such as mascara, eyeshadow, eye liner and other known make-up preparations; shampoosincluding clear liquids, liquid creams or lotions, solid creams or gels,oils, powders, aerosols, dry, conditioning, baby, anti-dandruff andmedicated, acid-balanced shampoos and other known shampoos; hair settingpreparations including lotions, sprays, dressings, brilliantines,fixatives, aerosols, emulsions, gels, and other known hair preparations;hair tonics and conditioners including rinses; hair colorants includingtemporary, semi-permanent, permanent or other hair dyes or colorants,hair dye removers, bleaches, lighteners and other known hair colorants;permanent wave and hair strengtheners; hair straighteners includingcaustic preparations, chemical hair reducing preparations and otherknown hair straighteners; dental products including dentifrices such astooth paste, tooth gels, tooth powders, solid dentifrice, denturecleansers, adhesives, and other known dental products; mouth washes; andother known personal care uses.

The glycosaminoglycan and cationic polymer combination of this inventionmay also be useful in applications other than kericare, such as varioustimed-release applications.

The glycosaminoglycan and cationic polymer, or both, may be provided insuitable carrier, including mixtures of carriers, which acts as a fluidvehicle for the glycosaminoglycan and/or cationic polymer, as well asfor suitable, optional ingredients. The type of carrier is not criticaland may be selected from any carrier suitable to the particularapplication. Illustrative carriers include, but are not limited to:water, such as deionized or distilled water; emulsions, such asoil-in-water or water-in-oil emulsions; alcohols, such as ethanol,isopropanol or the like; glycols, such as propylene glycol, glycerine orthe like; and mixtures thereof. Preferred carrier systems includewater-in-oil or oil-in-water emulsions, water, ethanol and aqueousethanol mixtures.

The glycosaminoglycan and cationic polymer combination may optionallycontain suitable ingredients or additives typical of kericarecompositions, which may be prepared following well established practicesin the art. Illustrative ingredients which may be suitable include, butmay not be limited to, the following, including mixtures thereof.

Illustrative surfactants may include: anionics such as fatty acid soaps,alkyl sulfates, alkyl ether sulfates, alkyl aryl sulfonates,sarcosinates, alkyl glucose esters or their alkoxylates and preferablysodium lauryl sulfate, ammonium lauryl sulfate, triethanol amine laurylsulfate, sodium laureth sulfate, triethanol amine stearate, methylglucose stearates or their ethoxylates and glycerol monostearate;nonionics such as fatty acid alkanol amides, alkyl aryl polyglycolether, polyglycol ethers and preferably cocamide DEA, nonoxynol-7 andoctoxynol-9; cationics such as alkyl trimethyl ammonium salts,quaternized amides of ethylene diamine, alkyl pyridinium salts andpreferably cetrimonium chloride, stearalkonium chloride and cetylpyridinium chloride; and amphoterics such as alkyl β-aminopropionates,betaines, alkyl imidazolines and preferably cocamidopropyl betaine andcaproamphocarboxypropionate. Illustrative cleansers may include naturaloils and alcohols and preferably mineral oil, lanolin oil, ethanol andisopropanol. Illustrative colorants may include pigments, dyes, andpreferably FD&C Blue No. 1, FD&C No. 1 Aluminum Lake or similar sets ofgreen, red or yellow. Illustrative preservatives may include alcohols,aldehydes, p-hydroxybenzoates and preferably methylparaben,propylparaben, glutaraldehyde and ethyl alcohol. Illustrativemoisturizers may include alkyl glucose alkoxylates or their esters,fatty alcohols, fatty esters, glycols and preferably methyl glucoseethoxylates or propoxylates and their stearate esters, isopropylmyristate, lanolin or cetyl alcohols, propylene glycol, glycerol andsorbitol. Illustrative pH adjustors may include inorganic and organicacids and bases and preferably aqueous ammonia, citric acid, phosphoricacid, acetic acid, triethanolamine and sodium hydroxide. Illustrativeemulsifiers may include anionic and nonionic surfactants and preferablystearic acid, glycerol monostearate, cocoyl diethanolamide, and thepreferred anionic and nonionic surfactants listed previously.Illustrative propellants may include hydrocarbons, fluorocarbons,ethers, carbon dioxide, nitrogen and dimethyl ether. Illustrativereducing agents may include ammonium thioglycolate and sodiumthioglycolate. Illustrative thickeners may include sodium chloride,hydroxyethyl cellulose, hydroxypropyl methyl cellulose, sodiumcarboxymethyl cellulose and polymers containing hydrophobe bunchesincluding hydrophobe modified polyurethanes or other such polymersdescribed in U.S. Pat. No. 4,426,485.

Other typical ingredients may include, but may not be limited to, thefollowing: fragrances; foaming agents; sunscreen and suntan agents;depilatory agents; flavors; astringent agents; antiseptics; deodorants;antiperspirants; insect repellants; bleaches and lighteners;anti-dandruff agents; adhesives; polishes; strengtheners for hair,nails, or the like; fillers; barrier materials; and other known kericareadditives. Mixtures of such ingredients may also be provided.

The amount of optional ingredients contained in the combinations of thisinvention is not critical but will vary depending upon the particularingredient, composition and desired use level and may be any effectiveamount for achieving the desired property provided by such ingredients,following well established procedures known to those in the art.

Compositions of glycosaminoglycan and cationic polymer combination ofthis invention may be produced by providing the glycosaminoglycan orcationic polymer, or both, along with optional ingredients, such as anyone or more suitable ingredients as previously described, to one or moresuitable carriers. The glycosaminoglycan and cationic polymer may beprovided comprising or consisting essentially of both components eitherseparately as two compositions or combined in a single composition. Whenused separately, the glycosaminoglycan may be applied eithersimultaneously or sequentially to the application of cationic polymer.Typically, the cationic polymer is provided prior to, or along with, theapplication glycosaminoglycan.

The following examples are presented as illustrative embodiments of thisinvention and are not intended to limit the scope thereof. Unless statedotherwise all percentages are given in weight percent.

EXAMPLES

The various designations used in the examples are defined as follows:

    ______________________________________                                        Designation                                                                            Description                                                          ______________________________________                                        Anionic  Sodium salt of carboxymethyl cellulose                               Polymer I                                                                              having a degree of carboxymethyl                                              substitution of between 0.4-1.0 and a                                         2 wt. % Brookfield viscosity of between                                       200-800 cP.                                                          Cationic N--dodecyl, N,N--dimethyl quaternary                                 Polymer I                                                                              ammonium chloride substituted                                                 hydroxyethyl cellulose, having a degree                                       of cationic substitution of                                                   approximately 0.1, a 1 wt. % aqueous                                          solution viscosity of 150-300 cP                                              (Brookfield Model LVT, Spindle #2, 60                                         rpm) and an ash content (NaCl) of about                                       3 wt. %.                                                             Cationic A graft copolymer of hydroxyethyl                                    Polymer II                                                                             cellulose and dimethyl diallyl ammonium                                       chloride, having a CTFA designation of                                        Polyquaternium-4, available from                                              National Starch under the trademark                                           CELQUAT ® Polymer, grade H-100.                                  Cationic A graft copolymer of hydroxethyl                                     Polymer III                                                                            cellulose and dimethyl diallyl ammonium                                       chloride, having a CTFA designation of                                        Polyquaternium-4, available from                                              National Starch under the trademark                                           CELQUAT ® Polymer, grade L-200.                                  Cationic A copolymer of vinyl pyrrolidone and                                 Polymer IV                                                                             diethylsulfate quaternized                                                    dimethylaminoethyl methacrylate, having                                       a CTFA designation of Polyquaternium-11,                                      available from GAF Corp. under the                                            trademark GAFQUAT ® Polymer, grade                                        755N.                                                                Cationic A homopolymer of dimethyl diallyl                                    Polymer V                                                                              ammonium chloride, having a CTFA                                              designation of Polyquaternium-6,                                              available from Calgon Corp. under the                                         trademark MERQUAT ® Polymer, grade 100.                          Cationic A copolymer of acrylamide and dimethyl                               Polymer VI                                                                             diallyl ammonium chloride, having a                                           CTFA designation of Polyquaternium-7,                                         available from Calgon Corp. under the                                         trademark MERQUAT ® Polymer, grade 550.                          Cationic N,N,N--trimethyl ammonium chloride                                   Polymer VII                                                                            substituted hydroxethyl cellulose,                                            having a 2 wt. % Brookfield viscosity                                         of between 300-500 cP and a wt. % N of                                        about 0.8-1.1                                                        Cationic N,N,N--trimethyl ammonium chloride                                   Polymer VIII                                                                           substituted hydroxethyl cellulose,                                            havin a 2 wt. % Brookfield viscosity                                          of between 300-500 cP and a wt. % N of                                        about 1.8.                                                           Glycosam-                                                                              Sodium salt of hylan, produced by in                                 inoglycan I                                                                            situ reaction of aldehyde with                                                naturally occurring hyaluronan in                                             rooster comb following the procedures                                         described in U.K. Published Patent                                            Application No. 2,172,295A, having a                                          viscosity number in excess of 4,000 cc                                        per gram (measured at 80 μg per ml.                                        of glycosaminoglycan in a 0.15 N sodium                                       chloride solvent at 25° C., available                                  from Biomatrix, Inc. under the                                                trademark HYLADERM ®.                                            Glycosam-                                                                              Sodium salt of hyaluronan having a                                   inoglycan II                                                                           viscosity number in excess of 4,000 cc                                        per gram (measured at 80 μg per ml.                                        of glycosaminoglycan in a 0.15 N sodium                                       chloride solvent at 25° C.), available as                              an 0.5-0.6 wt. % aqueous solution in                                          admixture with proteins and other                                             naturally occuring substances, as                                             described in U.S. Pat. No. 4,303,676                                          (Balazs), available from Biomatrix,                                           Inc. under the trademark BIOMATRIX ®                                      HA.                                                                  Glycosamin-                                                                            Heparin available from Sigma Chemical                                oglycan III                                                                            Co.                                                                  Glycosamin-                                                                            Chondroitin sulfate available from                                   oglycan IV                                                                             Sigma Chemical Co.                                                   Nonionic Hydroxyethyl cellulose having a hydroxy-                             Polymer I                                                                              ethyl molar substitution of between                                           2.0-2.5 and having a 2 wt. % Brookfield                                       viscosity of between 300-400 cP,                                              available from Union Carbide Corp.                                            under the trademark CELLOSIZE ® QP-300.                          Preserva-                                                                              A 27-29 wt. % solution of mixed esters                               tive I   of methyl, ethyl, propyl and butyl                                            paraben in phenoxyethanol solvent,                                            available from Nipa Laboratories under                                        the trademark PHENONIP ®.                                        Preserva-                                                                              N--(hydroxymethyl)-N--(1,3-dihydroxymethyl-                          tive II  2,5-dioxo-4-imidazolidinyl)-N'--                                              (hydroxymethyl) urea, having a CTFA                                           designation of Diazolidinyl urea,                                             available from Sutton Laboratories                                            under the trademark GERMALL ® II.                                Solvent I                                                                              Phenoxyethanol.                                                      Surfactant                                                                             Sodium laureth-3 sulfate available from                              I        Henkel Corp. as 28.5 wt. % aqueous                                            solution under the trademark STANDAPOL                                        ES 3.                                                                Surfactant                                                                             A 9-10 mole (average) ethoxylate of                                  II       p-(1,1,3,3-tetramethylbutyl) phenol                                           available from Aldrich Chemical Co.                                           under the trademark TRITON ® X-100.                              Surfactant                                                                             A cocoamphocarboxypropionate, available                              III      from Miranol Corp. as a 39 wt. %                                              aqueous solution under the trademark                                          MIRANOL ® C2M-SF Concentrate.                                    Surfactant                                                                             A 20 mole (average) ethoxylate of                                    IV       9-octadecen-ol, having a CTFA                                                 designation of Oleth-20, available from                                       Amerchol Corp. under the trademark                                            AMEROXOL ® OE-20.                                                Surfactant                                                                             A cocobetaine, available from                                        V        Henkel Corp. as a 43.5 wt. % aqueous                                          solution under the trademark                                                  VELVETEX ® AB-45.                                                Surfactant                                                                             A 20 mole (average) ethoxylate of methyl                             VI       glucose sesquistearate, having a CTFA                                         designation of Methyl gluceth-20                                              sesquistearate, available from Amerchol                                       Corp. under the trademark GLUCAMATE ®                                     SSE-20.                                                              Surfactant                                                                             A 16 mole (average) ethoxylate of                                    VII      lanolin alcohol, having a CTFA                                                designation of Laneth-16, available                                           from Amerchol Corp. under the trademark                                       SOLULAN ® 16.                                                    Surfactant                                                                             A 9 mole (average) ethoxylate of a                                   VIII     mixture of C.sub.11-15 alkanols, available                                    from Union Carbide Corp. under the                                            trademark TERGITOL ® 15-S-9.                                     Scintilla-                                                                             A toluene solution containing fluors                                 tion     and balancing acidic solubilizer,                                    Complement                                                                             available from Isolab, Inc. under the                                         tradename Unisol ® Complement.                                   Tissue   A quaternary ammonium hydroxide                                      Solubilizer                                                                            available from Isolab, Inc. under the                                         tradename Unisol ®                                               ______________________________________                                    

Unless otherwise indicated, the following test procedures are used tomeasure product and performance characteristics listed in the examples.

Compatibility: After cleared of air bubbles by centrifugation at 2000rpm for 10 minutes, samples of aqueous solutions of glycosaminoglycanand cationic polymer combinations are measured for visible absorbanceimmediately after preparation of the solution, at a wavelength of 540nanometers using distilled water as a control. The samples, in cuvettes,are then covered and refrigerated. At least one day later, the cuvettesare allowed to return to room temperature and the absorbancemeasurements are repeated. Compatibility is generally demonstrated bythe absence of a significant drop in absorbance in the repeatmeasurement due to precipitation or coacervation.

Feel: A small amount of designated test composition is applied to thevolar forearm, preferably at a hairless site, or to the back of thehand, keeping the test site consistent between comparisons, and rubbedinto the skin. The characteristics of the composition which areevaluated include feel, rub-in, afterfeel of the treated skin,appearance of skin, along with any other noted characteristics.

Hair substantivity: Two procedures are used to determine hairsubstantivity.

1. Prior to using radiolabelled glycosaminoglycan, samples of blondehair are prepared by washing in Surfactant II, followed by rinsing wellfirst with tap water and then 3 times with distilled water. The hairsamples are allowed to air dry and are cut into approximately 1 cmpieces. Samples of 100 mg of hair are placed in 7 ml glass scintillationvials and 1.0 ml of designated test solution of radiolabelledglycosaminoglycan is added to the sample vial followed by incubation for1 hour with shaking. After the test solution is removed, the sample hairis rinsed 3 times with 5 ml distilled water per rinse. One ml of TissueSolubilizer is added and the sample allowed to stand overnight at roomtemperature. The solubilized hair sample is transferred to a 20 ml glassscintillation vial with 0.5 ml methanol then 10 ml of ScintillationComplement is added. The radioactivity of the solubilized hair sample ismeasured using a ISOCAP® 300 liquid scintillation counter. The amount ofglycosaminoglycan bound to the hair is presented as the percent of thedisintegrations per minute, i.e. DPM, applied to the hair which ismeasured on washed and solubilized hair solution. Sequential testing isevaluated using the same procedure except that two designated textsolutions, one of cationic polymer and the other of glycosaminoglycan,are used in a two step process. In the first step, the first designatedtest solution is incubated with shaking for 15 minutes, followed byrinsing the hair sample 3 times with 5 ml distilled water per rinse. Thesecond step consists of adding 1 ml of the second designated testsolution and then proceeding with 1 hour incubation and so on asdescribed in the original procedure.

2. Using electrokinetic streaming potential analysis, a 6.6 g. sample ofvirgin hair is divided into 3 bundles. Each hair bundle is prepared fortreatment by thoroughly wetting with tap water, applying 3 drops ofSurfactant VIII which is manually worked into the hair for 30 secondsfollowed by rinsing first with tap water and then double distilledwater. Samples of 1"-1.5" sections are cut, covered with doubledistilled water in crystallizing dishes and swirled around to insure theabsence of air bubbles. The hair samples are placed in the bottomcompartment of a U-shaped section of cell with air bubbles tapped outusing a wire probe, and contained in the cell using porous platinum discelectrodes. The samples are rinsed 3 times with 100 ml of doubledistilled water per rinse using an aspirator to drain off liquid. Thecells are filled with a weak electrolyte solution of 10⁻⁴ N KNO₃, whichis passed through the hair for 5-minutes cycles and the streamingpotential is measured to determine the zeta potential of the clear hair.The electrolyte solution is removed through aspiration and the cellfilled with 300 ml of designated treating solution containingpolymer(s). After 25 minutes of exposure to the treating solution, toallow adsorption of the polymers onto the hair to take place, thestreaming potential is measured while passing the solution through thecell for 5 1-minute cycles to determine the zeta potential of haircovered with adsorbed polymers while still in contact with the polymersolution (Step 1). The treating solution is removed through aspirationand the hair rinsed 3 times with 100 ml of double distilled water perrinse and removed using aspiration after each cycle (Step 2). The cellis filled with 300 ml of 10⁻⁴ N KNO₃ solution (Step 3). The solution ispassed back and forth through the hair for 1 hour with streamingpotential measurements taken over this time period to determine theretention of adsorbed polymer on rinsing. Sequential polymer applicationis analyzed using the same procedure (Steps 1 and 2 above) except that asingle polymer pre-treating solution is used. After rinsing (Step 2) thecell is filled with the second designated polymer treating solutionafter which the streaming potential is measured for one hour (Step 3).The electrokinetic (zeta) streaming potential is determined followingestablished procedures, such as described in a paper by P. Somasundaranet al. in the Journal of Colloid Interface Science, Volume 45, page 591(1973).

Modulus of elasticity: Measurements of designated test solutions aremade over a frequency range of from 0.01 Hz to 5.0 Hz, using anoscillation strain amplitude of 5, performed at 25° C. using a BohlinVOR rheometer equipped with a C-14 cup and spindle.

Shear viscosity: Measurements are made over a shear range of from 0.05sec⁻¹ to 100 sec⁻¹, performed at 25° C. using a Bohlin VOR rheometerequipped with a C-14 cup and spindle.

Skin substantivity: Two procedures are used to determine skinsubstantivity.

1. Dried samples of stratum corneum taken from the skin of neonatalrats, having an average weight of 25 mg, are placed in 60 mm petridishes, using 4 petri dishes per group totaling 100 mg stratum corneum.Two ml of designated test solution containing radiolabelledglycosaminoglycan are added to each petri dish which is incubated for 1hour with gentle shaking. The test solution is then removed and thestratum corneum washed 3 times with 5 ml distilled water. All 4 stratacorneum from each group are placed into a 20 ml glass scintillation vialalong with 1 ml of Tissue Solubilizer added and allowed to standovernight at room temperature. One-half ml of methanol then 10 ml ofScintillation Complement are added to the vials. The radiolabelledglycosaminoglycan bound to the solubilized tissue samples is measuredusing an ISOCAP® 300 liquid scintillation counter. The weight, inmicrograms (μg), of bound glycosaminoglycan is calculated from themeasured radioactivity of the treated strata corneum and the measuredspecific activity of the radiolabelled glycosaminoglycan in DPM per μg.Sequential polymer application is analyzed using the same procedureexcept for the following modification: instead of a single 2 ml additionof test solution, 2 ml of first test solution is added to each petridish followed by incubation for 30 minutes with gentle shaking. Thestrata corneum are then washed 3 times with distilled water and 2 ml ofsecond test solution is added followed by 1 hour incubation and so on asin the original procedure.

2. Using electron spectroscopy, samples of strata corneum, treatedsubstantially as described previously and air dried on TEFLON® surface,are cut into approximately 1/2×1/2 inch squares and clamped to a sampleplatter using an aluminum mask. A 1×2 mm area is analyzed using standardelectron spectroscopyic procedures such as described by M. K. Bahl, inthe Journal of Society of Cosmetic Chemists, Volume 36, pages 287-296(1985) and by E. D. Goddard and W. C. Harris, in the Proceedings of theFourteenth Congress of the International Federation of Societies ofCosmetic Chemists (I.F.S.C.C.), Barcelona, Spain, Volume 2, 1039(September 1986). Spectral measurements are made using a Surface ScienceInstruments SSX-100 Small Spot ESCA spectrometer equipped with a lowenergy electron flood gun used to provide charge neutralization for theelectrically non-conductive samples and following the manufacturer'sprocedures and specifications. The data is acquired using an analyzerpass energy of 150 eV for a survey spectra and 50 eV for high resolutionspectra. Elemental compositions are calculated, peak fitting of highresolution spectra are made and angular measurements using tilt stagemountings are provided following the manufacturer's specifications.

Stability: Absorbance and rheological properties are measured fordesignated test solutions over various periods of time and temperatureconditions using the previously described procedures. Freeze-thawstability is determined for designated test solutions subjected to 3cycles of freezing at -20° C. overnight followed by thawings, withmeasurements then taken using the previously described test procedures.

EXAMPLE 1 Preparation of Cationic Polymer and GlycosaminoglycanCombinations

Unless otherwise indicated, aqueous solutions are prepared by adding thedesignated cationic polymer, glycosaminoglycan and/or other ingredientsto distilled water, at the concentrations and using the components asset forth in Table I.

                                      TABLE I                                     __________________________________________________________________________    EXAMPLE 1: SAMPLE COMBINATIONS                                                Cationic  Glycosam-           Other                                           Polymer   inoglycan                                                                             Weight                                                                            Surfactant                                                                            Ingredients                                     Run                                                                              Type                                                                             Wt. %                                                                             Type                                                                             Wt. %                                                                              Ratio.sup.a                                                                       Type                                                                             Wt. %                                                                              Type Wt. %                                      __________________________________________________________________________    A     --  I  0.001                                                                              --     --                                                   1-1                                                                              I  0.01                                                                              I  0.001                                                                              10:1   --        --                                         1-2                                                                              I  0.015                                                                             I  0.001                                                                              15:1   --        --                                         1-3                                                                              I  0.02                                                                              I  0.001                                                                              20:1   --        --                                         1-4                                                                              I  0.025                                                                             I  0.001                                                                              25:1   --        --                                         1-5                                                                              I  0.05                                                                              I  0.001                                                                              50:1   --        --                                         1-6                                                                              I  0.035                                                                             I  0.001                                                                              35:1   --        --                                         1-7                                                                              I  0.050                                                                             I  0.001                                                                              50:1   --        --                                         1-8                                                                              I  0.100                                                                             I  0.001                                                                              100:1  --        --                                         1-9                                                                              I  0.01                                                                              I  0.001.sup.b                                                                        10:1   --        --                                         B     --  I  0.0005                                                                             --     --        --                                         2-1                                                                              I  0.005                                                                             I  0.0005                                                                             10:1   --        --                                         2-2                                                                              I  0.125                                                                             I  0.0005                                                                             25:1   --        --                                         3-C   --  I  0.001                                                                              --  I  0.0006    --                                         3-1                                                                              I  0.01                                                                              I  0.001                                                                              10:1                                                                              I  0.0006    --                                         3-2                                                                              I  0.025                                                                             I  0.001                                                                              25:1                                                                              I  0.0006    --                                         4-C   --  I  0.001                                                                              --  II 10        --                                         4-1                                                                              I  0.01                                                                              I  0.001                                                                              10:1                                                                              II 10        --                                         4-2                                                                              I  0.025                                                                             I  0.001                                                                              25:1                                                                              II 10        --                                         5-1                                                                              II 0.001                                                                             I  0.001                                                                               1:1   --        --                                         5-2                                                                              II 0.005                                                                             I  0.001                                                                               5:1   --        --                                         5-3                                                                              II 0.009                                                                             I  0.001                                                                               9:1   --        --                                         5-4                                                                              II 0.01                                                                              I  0.001                                                                              10:1   --        --                                         5-5                                                                              II 0.025                                                                             I  0.001                                                                              25:1   --        --                                         6-C   --  I  0.001                                                                              --  III                                                                              0.10      --                                         6-1                                                                              I  0.01                                                                              I  0.001                                                                              10:1                                                                              III                                                                              0.10      --                                         6-2                                                                              I  0.025                                                                             I  0.001                                                                              25:1                                                                              III                                                                              0.10      --                                         6-3                                                                              I  0.01                                                                              I  0.001                                                                              10:1                                                                              III                                                                              0.002     --                                         C  -- I   0.01                                                                             --       --      --                                              7-1                                                                              I  0.2 I  0.01 .sup. 20:1.sup.b                                                                     --        --                                         7-2                                                                              I  0.2 I  0.01 20:1   --        --                                         7-3                                                                              I  0.15                                                                              I  0.01 15:1   --        --                                         8-1                                                                              I  0.018                                                                             I  0.0007                                                                             25:1   --        --                                         8-2                                                                              I  0.018                                                                             I  0.0007                                                                             25:1                                                                              I  0.0003    --                                         8-3                                                                              I  0.018                                                                             I  0.0007                                                                             25:1                                                                              I  0.0007    --                                         8-4                                                                              I  0.018                                                                             I  0.0007                                                                             25:1                                                                              I  0.0014    --                                         8-5                                                                              I  0.018                                                                             I  0.0007                                                                             25:1                                                                              I  0.0036    --                                         8-6                                                                              I  0.018                                                                             I  0.0007                                                                             25:1                                                                              I  0.0071    --                                         9  I  0.018                                                                             I  0.0007                                                                             25:1   --   API.sup.c                                                                          0.0007                                     10 I  0.025                                                                             I  0.001                                                                              25:1                                                                              IV 0.001     --                                         11 I  0.025                                                                             I  0.001                                                                              25:1   --   PI.sup.d                                                                           0.003                                      12 I  0.025                                                                             I  0.001                                                                              25:1                                                                              I  0.002     --                                         13 I  0.025                                                                             I  0.001                                                                              25:1   --   Ethanol                                                                            25                                         13-2                                                                             I  0.025                                                                             I  0.001                                                                              25:1   --   Ethanol                                                                            25,                                                                 --   NPI.sup.e                                                                          0.05                                       14-1                                                                             I  0.025                                                                             I  0.001                                                                              25:1                                                                              V  7.5       --                                         14-2                                                                             I  0.025                                                                             I  0.001                                                                              25:1                                                                              V  7.5,                                                                       I  0.002     --                                         14-3                                                                             I  0.025                                                                             I  0.001                                                                              25:1                                                                              IV 5         --                                                               I  0.002                                                15 I  0.01                                                                              III                                                                              0.001                                                                              .sup. 10:1.sup.b                                                                     --        --                                         16 I  0.01                                                                              IV 0.001                                                                              .sup. 10:1.sup.b                                                                     --        --                                         D  I  0.01   --   --     --        --                                         E     --  I  0.0038                                                                             --     --        --                                         F  I  0.095  --   --     --        --                                         17-1                                                                             I  0.095                                                                             I  0.0038                                                                             .sup. 25:1.sup.b                                                                     --        --                                         17-2                                                                             I  0.095                                                                             I  0.0038                                                                             25:1   --        --                                         18-C                                                                             I  1      --   --     --        --                                         18-1                                                                             I  1   I  0.01 100:1  --        --                                         18-2                                                                             I  1   I  0.02 50:1   --        --                                         18-3                                                                             I  1   I  0.03 33:1   --        --                                         18-4                                                                             I  1   I  0.04 25:1   --        --                                         18-5                                                                             I  1   I  0.05 20:1   --        --                                         18-6                                                                             I  1   I  0.06 16:1   --        --                                         18-7                                                                             I  1   I  0.07 14:1   --        --                                         18-8                                                                             I  1   I  0.08 12:1   --        --                                         18-9                                                                             I  1   I  0.09 11:1   --        --                                         18-10                                                                            I  1   I  0.10 10:1   --        --                                         19-C                                                                             I  2      --   --     --        --                                         19-1                                                                             I  2   I  0.20 100:1  --        --                                         19-2                                                                             I  2   I  0.04 50:1   --        --                                         19-3                                                                             I  2   I  0.06 33:1   --        --                                         19-4                                                                             I  2   I  0.08 25:1   --        --                                         19-5                                                                             I  2   I  0.10 20:1   --        --                                         19-6                                                                             I  2   I  0.12 16:1   --        --                                         19-7                                                                             I  2   I  0.14 14:1   --        --                                         19-8                                                                             I  2   I  0.16 12:1   --        --                                         19-9                                                                             I  2   I  0.18 11:1   --        --                                         19-10                                                                            I  2   I  0.20 10:1   --        --                                         20-1                                                                             I  0.2 I  0.002                                                                              100:1  --        --                                         20-2                                                                             I  0.2 I  0.006                                                                              33:1   --        --                                         20-3                                                                             I  0.2 I  0.010                                                                              20:1   --        --                                         20-4                                                                             I  0.2 I  0.016                                                                              12:1   --        --                                         20-5                                                                             I  0.2 I  0.020                                                                              10:1   --        --                                         21-1                                                                             I  2   II 0.02 100:1  --        --                                         21-2                                                                             I  2   II 0.06 33:1   --        --                                         21-3                                                                             I  2   II 0.10 20:1   --        --                                         21-4                                                                             I  2   II 0.12 17:1   --        --                                         21-5                                                                             I  2   II 0.16 12:1   --        --                                         21-6                                                                             I  2   II 0.20 10:1   --        --                                         22-C                                                                             I  0.2 II --   --     --        --                                         22-1                                                                             I  0.2 II 0.002                                                                              100:1  --        --                                         22-2                                                                             I  0.2 II 0.006                                                                              33:1   --        --                                         22-3                                                                             I  0.2 II 0.010                                                                              20:1   --        --                                         22-4                                                                             I  0.2 II 0.012                                                                              17:1   --        --                                         22-5                                                                             I  0.2 II 0.016                                                                              12:1   --        --                                         22-6                                                                             I  0.2 II 0.020                                                                              10:1   --        --                                         23-C                                                                             II 2      --   --     --        --                                         23-1                                                                             II 2   I  0.02 100:1  --        --                                         23-2                                                                             II 2   I  0.06 33:1   --        --                                         23-3                                                                             II 2   I  0.10 20:1   --        --                                         23-4                                                                             II 2   I  0.14 14:1   --        --                                         23-5                                                                             II 2   I  0.18 11:1   --        --                                         23-6                                                                             II 2   I  0.22  9:1   --        --                                         23-C'                                                                            II 0.2    --   --     --        --                                         23-7                                                                             II 0.2 I  0.002                                                                              100:1  --        --                                         23-8                                                                             II 0.2 I  0.006                                                                              33:1   --        --                                         23-9                                                                             II 0.2 I  0.010                                                                              20:1   --        --                                         23-10                                                                            II 0.2 I  0.014                                                                              14:1   --        --                                         23-11                                                                            II 0.2 I  0.018                                                                              11:1   --        --                                         23-12                                                                            II 0.2 I  0.022                                                                               9:1   --        --                                         24-C                                                                             III                                                                              2      --   --     --        --                                         24-1                                                                             III                                                                              2   I  0.02 100:1  --        --                                         24-2                                                                             III                                                                              2   I  0.06 33:1   --        --                                         24-3                                                                             III                                                                              2   I  0.10 20:1   --        --                                         24-4                                                                             III                                                                              2   I  0.14 14:1   --        --                                         24-5                                                                             III                                                                              2   I  0.18 11:1   --        --                                         24-6                                                                             III                                                                              2   I  0.22  9:1   --        --                                         24-C'                                                                            III                                                                              0.2    --   --     --        --                                         24-7                                                                             III                                                                              0.2 I  0.002                                                                              100:1  --        --                                         24-8                                                                             III                                                                              0.2 I  0.006                                                                              33:1   --        --                                         24-9                                                                             III                                                                              0.2 I  0.010                                                                              20:1   --        --                                         24-10                                                                            III                                                                              0.2 I  0.014                                                                              14:1   --        --                                         24-11                                                                            III                                                                              0.2 I  0.018                                                                              11:1   --        --                                         24-12                                                                            III                                                                              0.2 I  0.022                                                                               9:1   --        --                                         25-C                                                                             IV 1      --   --     --        --                                         25-1                                                                             IV 1   I  0.02 50:1   --        --                                         25-2                                                                             IV 1   I  0.06 16:1   --        --                                         25-3                                                                             IV 1   I  0.10 10:1   --        --                                         25-4                                                                             IV 1   I  0.14  7:1   --        --                                         25-5                                                                             IV 1   I  0.18 5.6:1  --        --                                         25-C'                                                                            IV 0.1    --   --     --        --                                         25-6                                                                             IV 0.1 I  0.002                                                                              50:1   --        --                                         25-7                                                                             IV 0.1 I  0.006                                                                              16:1   --        --                                         25-8                                                                             IV 0.1 I  0.010                                                                              10:1   --        --                                         25-9                                                                             IV 0.1 I  0.014                                                                               7:1   --        --                                         25-10                                                                            IV 0.1 I  0.018                                                                              5.6:1  --        --                                         26 I  0.5 I  various                                                                            --     --        --                                         27 I  1   I  various                                                                            --     --        --                                         28 I  2   I  various                                                                            --     --        --                                         29 V  2   I  various                                                                            --     --        --                                         30 VI 2   I  various                                                                            --     --        --                                         31 VII                                                                              1   I  various                                                                            --     --        --                                         32 VIII                                                                             2   I  various                                                                            --     --        --                                         33-1                                                                             I  2   I  0.2  10:1                                                                              VI 0.1       --                                         33-2                                                                             I  2   I  0.2  10:1                                                                              VI 1.0       --                                         33-3                                                                             I  2   I  0.2  10:1                                                                              VI 5.0       --                                         33-4                                                                             I  0.2 I  0.02 10:1                                                                              VI 0.01      --                                         33-5                                                                             I  0.2 I  0.02 10:1                                                                              VI 0.10      --                                         33-6                                                                             I  0.2 I  0.02 10:1                                                                              VI 0.50      --                                         34-1                                                                             I  2.5 I  0.1  25:1                                                                              -- --        --                                         34-2                                                                             I  2.5 I  0.1  25:1                                                                              V1 0.1       --                                         34-3                                                                             I  2.5 I  0.1  25:1                                                                              VI 1.0       --                                         34-4                                                                             I  2.5 I  0.1  25:1                                                                              VI 5.0       --                                         34-5                                                                             I  0.25                                                                              I  0.01 25:1                                                                              -- --        --                                         34-6                                                                             I  0.25                                                                              I  0.01 25:1                                                                              VI 0.01      --                                         34-7                                                                             I  0.25                                                                              I  0.01 25:1                                                                              VI 0.10      --                                         34-8                                                                             I  0.25                                                                              I  0.01 25:1                                                                              VI 0.05      --                                         35-1                                                                             I  2   I  0.2  10:1                                                                              VII                                                                              0.1       --                                         35-2                                                                             I  2   I  0.2  10:1                                                                              VII                                                                              1.0       --                                         35-3                                                                             I  2   I  0.2  10:1                                                                              VII                                                                              5.0       --                                         35-4                                                                             I  0.2 I  0.02 10:1                                                                              VII                                                                              0.01      --                                         35-5                                                                             I  0.2 I  0.02 10:1                                                                              VII                                                                              0.10      --                                         35-6                                                                             I  0.2 I  0.02 10:1                                                                              VII                                                                              0.50      --                                         36-1                                                                             I  2.5 I  0.1  25:1                                                                              VII                                                                              0.1       --                                         36-2                                                                             I  2.5 I  0.1  25:1                                                                              VII                                                                              1.0       --                                         36-3                                                                             I  2.5 I  0.1  25:1                                                                              VII                                                                              5.0       --                                         36-4                                                                             I  0.25                                                                              I  0.01 25:1                                                                              VII                                                                              0.01      --                                         36-5                                                                             I  0.25                                                                              I  0.01 25:1                                                                              VII                                                                              0.10      --                                         36-6                                                                             I  0.25                                                                              I  0.01 25:1                                                                              VII                                                                              0.50      --                                         37-1                                                                             I  2   I  0.2  10:1                                                                              IV 0.1       --                                         37-2                                                                             I  2   I  0.2  10:1                                                                              IV 1.0       --                                         37-3                                                                             I  2   I  0.2  10:1                                                                              IV 5.0       --                                         37-4                                                                             I  0.2 I  0.02 10:1                                                                              IV 0.01      --                                         37-5                                                                             I  0.2 I  0.02 10:1                                                                              IV 0.10      --                                         37-6                                                                             I  0.2 I  0.02 10:1                                                                              IV 0.50      --                                         38-1                                                                             I  2.5 I  0.1  25:1                                                                              IV 0.1       --                                         38-2                                                                             I  2.5 I  0.1  25:1                                                                              IV 1.0       --                                         38-3                                                                             I  2.5 I  0.1  25:1                                                                              IV 5.0       --                                         38-4                                                                             I  0.25                                                                              I  0.01 25:1                                                                              IV 0.01      --                                         38-5                                                                             I  0.25                                                                              I  0.01 25:1                                                                              IV 0.10      --                                         38-6                                                                             I  0.25                                                                              I  0.01 25:1                                                                              IV 0.50      --                                         39-1                                                                             I  0.25                                                                              I  0.025                                                                              10:1   --   PI.sup.d                                                                           0.03                                       39-2                                                                             I  0.25                                                                              I  0.025                                                                              10:1                                                                              III                                                                              0.4  PI.sup.d                                                                           0.03                                       39-3                                                                             I  0.25                                                                              I  0.025                                                                              10:1                                                                              III                                                                              1.0  PI.sup.d                                                                           0.03                                       39-4                                                                             I  0.25                                                                              I  0.025                                                                              10:1                                                                              III                                                                              2.0  PI.sup.d                                                                           0.03                                       39-5                                                                             I  0.25                                                                              I  0.025                                                                              10:1                                                                              III                                                                              3.0  PI.sup.d                                                                           0.03                                       39-6                                                                             I  0.25                                                                              I  0.025                                                                              10:1                                                                              III                                                                              4.0  PI.sup.d                                                                           0.03                                       G     --  I  0.02 --     --        --                                         H     --  I  0.04 --     --        --                                         I     --  I  0.1  --     --        --                                         I'    --  I  0.1  --     --        --                                         40-1                                                                             I  2.0 I  0.1  20:1   --   PI.sup. d                                                                          0.3                                        40-2                                                                             I  2.0 I  0.1  20:1   --   PII.sup.f                                                                          0.3                                        40-3                                                                             I  2.5 I  0.1  25:1   --   PI.sup.d                                                                           0.3                                        40-4                                                                             I  2.5 I  0.1  25:1                                                                              II 10   PI.sup.d                                                                           0.3                                        40-5                                                                             I  2.5 II 0.1  25:1   --   PI.sup.d                                                                           0.7                                        40-6                                                                             I  2.5 II 0.1  25:1                                                                              II 10   PI.sup.d                                                                           0.7                                        40-7                                                                             I  2.5 I  0.1  25:1   --        --                                         40-8                                                                             I  2.5 I  0.1  25:1   --   SI.sup.g                                                                           0.3                                        40-9                                                                             I  2.5 I  0.1  25:1   --   PI.sup.d                                                                           0.3                                        __________________________________________________________________________     Footnotes for Table I:                                                        .sup.a Relative weight ratio of cationic polymer to glycosaminoglycan.        .sup.b Cationic polymer applied initially followed by glycosaminoglycan       application.                                                                  .sup.c Anionic Polner I as described previously.                              .sup.d Preservative I as described previously.                                .sup.e Nonionic Polymer I as described previously.                            .sup.f Preservative II as described previously.                               .sup.g Solvent I as described previously.                                

EXAMPLE 2 Personal Care Formulations and Feel

In this example, personal care formulations containing cationic polymer,glycosaminoglycan and other personal care ingredients as listed in TableII are prepared using the following general procedures, unless otherwiseindicated. The designated formulation is generally provided by formingthe designated oil and water phases, except for the GERMABEN® IIE,Cationic Polymer I and Glycosaminoglycan I, and heating both phases to85° C. The water phase is added to the oil phase with vigorous stirring.The GERMABEN® IIE, when used, is then added at 75° C. followed byaddition of a 0.1% actives aqueous solution of Cationic Polymer I andGlycosaminoglycan I combination, provided at a weight ratio of cationicpolymer to glycosaminoglycan of 25:1, which is added to the designatedformulation at room temperature with thorough agitation.

Formulation 1: Dry Skin Lotion

A dry skin lotion, containing the concentration of ingredients listed inFormulation 1 of Table II, is prepared following the previouslydescribed general procedures except that the magnesium aluminum silicateis initially dispersed as a slurry in water at the designatedconcentration using high speed mixing.

Formulation 2: Moisturizing Lotion

A moisturizing lotion, containing the concentrations of ingredientsnoted in Formulation 2 of Table II, is prepared following the previouslydescribed general procedures.

Formulation 3: Hand Lotion

A hand lotion, containing the concentrations of ingredients listed inFormulation 3 of Table II, is prepared following the previouslydescribed general procedures, except that the oil and water phases areinitially heated to 75° C. instead of 85° C.

Formulation 4: Mild Lotion

A mild lotion, containing the concentrations of ingredients listed inFormulation 4 of Table II, is prepared following the previouslydescribed general procedures, except that the oil and water phases areinitially heated to 75° C. instead of 85° C. and the triethanolamine isadded at 75° C. after the water phase is added to the oil phase.

Formulation 5: Enriched Lotion

An enriched lotion, containing the concentrations of ingredients listedin Formulation 5 of Table II, is prepared following the previouslydescribed general procedures.

Formualtion 6: Dry Skin Cream

A dry skin cream, containing the concentrations of ingredients inFormulation 6 of Table II, is prepared as follows. Xanthan gum isdispersed in water with vigorous agitation at 70° C. The magnesiumaluminum silicate slurry is formed and heated to 70° C. with vigorousmixing. The oil phase ingredients are combined and heated to 70° C. Bothaqueous phases, i.e., xanthan and silicate, are added, one at a time, tothe oil phase with vigorous mixing. The GERMABEN® IIE is added followedby the previously described addition of Cationic Polymer I andGlycosaminoglycan I combination.

Formulation 7: Cleansing Cream

A cleansing cream, containing the concentrations of ingredients listedin Formulation 7 of Table II, is prepared following the previouslydescribed general procedures except that the oil and water phases areinitially heated to 80° C. instead of 85° C.

Formulation 8: Liquid Cream

A liquid cream, containing the concentrations of ingredients listed inFormulation 8 of Table II, is prepared using the previously describedgeneral procedures except as follows. The Carbomer 934 is initiallydispersed as a slurry in water with high speed agitation. Thetriethanolamine solution is added after obtaining a uniform mixture ofthe oil and water phases.

Formulation 9: Moisturizing Cream

A moisturizing cream, containing the concentrations of ingredientslisted in Formulation 9 of Table II, is prepared using the previouslydescribed general procedures except as follows. The oil and water phasesare initially heated to 75° C. instead of 85° C. The Carbomer 934 isinitially dispersed as a slurry in water with high speed agitation. Thetriethanolamine solution is added after obtaining a uniform mixture ofthe oil and water phases.

Formulation 10: All Purpose Cream

An all purpose cream, containing the concentrations of ingredientslisted in Formulation 10 of Table II, is prepared following thepreviously described general procedures.

Formulation 11: All-Purpose Skin Conditioning Lotion

An all purpose skin conditioning lotion, containing the concentrationsof ingredients listed in Formulation 11 of Table II, is preparedfollowing the previously described general procedures except that theCationic Polymer I and Glycosaminoglycan I combination is added at 40°C. while cooling to 30° C. instead of at room temperature.

Formulation 12: Conditioning and Styling Mousse

A conditioning and styling mousse, containing the concentration ofingredients listed in Formulation 12 of Table II, is prepared byinitially combining the ingredients of the water phase with mixing at75° C. until a uniform composition is obtained, followed by cooling to40° C. The alcohol phase is subsequently added at room temperaturefollowed by mixing until a uniform composition is obtained. The CationicPolymer I and Glycosaminoglycan I combination is then added, asgenerally described previously, with mixing until a uniform compositionis obtained. An aerosol composition is obtained by adding anisobutane/propane blend as propellant at a weight ratio of 9:1 offormulation to propellant.

                                      TABLE II                                    __________________________________________________________________________    PERSONAL CARE FORMULATION                                                                     Formulation No.                                               Ingredients:.sup.a                                                            (conc. in wt %) 1   2   3   4   5   6   7   8   9   10  11  12                __________________________________________________________________________    Oil Phase:                                                                    AMERCHOL ® L-101.sup.b                                                                    5.0                         5.0     5.0                       Petrolatum      5.0                 8.0                                       Mineral oil.sup.c                                                                             33.5    4.0 5.0 25.0                                                                              6.0 44.0.sup.z                                                                        3.5 2.0     2.0                   Lanolin.sup.d   3.0                                                           Sorbitan sesquioleate                                                                         2.5                                                           Beeswax (U.S.P.) 4.0                10.0                                      GLUCATE ® SS.sup.e                                                                        0.5         0.5                 0.5     2.0                   AMERLATE ® p.sup.f                                                                            0.5                 2.0 1.0                               Stearic acid        3.0         3.0         1.5                               Glyceryl stearate   2.0 4.0.sup.x                                                                             3.0     2.0 2.0                               SOLULAN ® 98.sup.g  2.0                                 2.0*              SOLULAN ® 5.sup.h   1.0     0.5                     0.5                   Cetyl alcohol           1.0 0.5     1.0         0.5 10.0                      GLUCAMATE ® SSE-20.sup.i                                                                              1.5     3.0         1.5     2.0                   Squalane                    0.9                                               SOLULAN ® C-24.sup.j        0.3                                           GLUCATE ® DO.sup.k              1.5                                       Isopropyl palmitate                 3.0                                       Stearyl alcohol                     2.0                                       Dimethicone                         0.5             1.0                       OHLAN ®.sup.1                       3.0                                   Ozokerite wax                           5.0                                   GLUCAM ® P-20 distearate.sup.m              4.0                           SOLULAN ® 16.sup.n                              3.0     1.5*              Myristyl myristate                                  5.0                       PROMULGEN ® G.sup.o                                 5.0                   Water Phase:                                                                  MgAl silicate.sup.p                                                                           12.5                25.0                                      Sodium borate   0.5                     0.6                                   GLUCAM ® E-20.sup.q                                                                       2.0 5.0                                                       GERMABEN ® IIE.sup.r                                                                      1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0                       Triethanolamine     1.0     3.0.sup.y                                                                         1.0         10.0.sup.y                                                                        3.0.sup.y                     Steapyrium chloride     0.1                                                   Glycerin                2.0                         2.5                       Carbomer 934.sup.s          10.0            10.0                                                                              10.0                          Propylene glycol                4.0         5.0                               Xanthan gum                         0.3                                       Methylbenzethonium chloride                         0.1                       GLUCAM ® E-10.sup.t                                 3.5                   GLUCAM ® P-10.sup.u                                     1.5               Cationic Polymer I                                                                            0.0962                                                                            0.0962                                                                            0.0962                                                                            0.0962                                                                            0.0962                                                                            0.0962                                                                            0.0962                                                                            0.0962                                                                            0.0962                                                                            0.0962                                                                            0.0962                                                                            0.125             Glycosaminoglycan I                                                                           0.0038                                                                            0.0038                                                                            0.0038                                                                            0.0038                                                                            0.0038                                                                            0.0038                                                                            0.0038                                                                            0.0038                                                                            0.0038                                                                            0.0038                                                                            0.0038                                                                            0.005             Water           q.s q.s q.s q.s q.s q.s q.s q.s q.s q.s q.s 73.0              Alcohol Phase:                                                                Ethyl alcohol.sup.v                                         15.0              AMERSETTE ® resin.sup.w                                 2.0               __________________________________________________________________________     Footnotes for Table II:                                                       .sup.a Unless otherwise indicated all trademark ingredients are available     from Amerchol Corp.                                                           .sup.b Blend of mineral oil and fraction of lanolin alcohol.                  .sup.c 70 SSU viscosity.                                                      .sup.d Anhydrous lanolin U.S.P., deoderized AAA.                              .sup.e Methyl glucose sesquistearate.                                         .sup.f Isopropyl lanolate.                                                    .sup.g Blend of polysorbate80, cetyl acetate and acetylated lanolin           alcohol.                                                                      .sup.h Blend of laneth5, ceteth5, oleth5 and steareth5.                       .sup.i PEG20 methyl glucose sesquistearate.                                   .sup.j Blend of choleth24 and ceteth24.                                       .sup.k Methyl glucose dioleate.                                               .sup.l Hydroxylated lanolin.                                                  .sup.m PPG20 methyl glucose ether distearate.                                 .sup.n Blend of laneth16, ceteth16, oleth16 and steareth16.                   .sup.o Blend of stearyl alcohol and ceteareth20.                              .sup.p 4% aqueous solution of magnesium aluminum silicate.                    .sup.q Methyl gluceth20.                                                      .sup.r Blend of propylene glycol, diazolidinyl urea, methylparaben and        propylparaben, available from Sutton Laboratories.                            .sup.s 3% aqueous solution of crosslinked polyacrylic acid.                   .sup.t Methyl gluceth10.                                                      .sup.u PPG10 methyl glucose ether.                                            .sup.v Specially denatured, #40.                                              .sup.w Copolymer of methacrylol ethyl betaine and methacrylates.              .sup.x Blend of glyceryl stearate and PEG100 stearate.                        .sup.y 10% aqueous solution.                                                  .sup.z 8090 SSU viscosity.                                                    *Provided in water phase (no oil phase).                                 

Using the previously described procedures, the feel of each formulationis evaluated as providing superior afterfeel properties. Theseformulations provide comparable feel and afterfeel properties toidentical formulations except which contain 0.05 wt. % GlycosaminoglycanI in place of the designated cationic polymer and glycosaminoglycancombinations. Comparable feel properties are not provided by equivalentformulations containing an equal or greater concentration of thedesignated cationic polymer only. These results demonstrate that lowconcentrations of glycosaminoglycan, when combined with the designatedcationic polymer, exhibit superior feel properties comparable to theproperties provided by much higher concentrations of glycosaminoglycanwhen no cationic polymer is present.

EXAMPLES 3-4 Hair Treatment and Substantivity EXAMPLE 3 HairSubstantivity Using Radiolabelled Glycosaminoglycan.

In this example the substantivity of the designated test solutions,using radiolabelled glycosaminoglycan, is evaluated using the previouslydescribed procedures with the results set forth in Table III.

                  TABLE III                                                       ______________________________________                                        EXAMPLE 3: HAIR SUBSTANTIVITY MEASUREMENTS                                    USING RADIOLABELLED GLYCOSAMINOGLYCAN                                                             Amount of Bound                                           Test         Run    Glycosaminoglycan                                         No.          No.    (% DPM*)                                                  ______________________________________                                        1            A      17/13                                                     2            1-1    64/79                                                     3            1-2    15/--                                                     4            1-3     9/--                                                     5            1-4     7/10                                                     6            1-5    --/5                                                      7            3-C    9                                                         8            3-1    53                                                        9            3-2    8                                                         10           4-C    2                                                         11           4-1    12                                                        12           4-2    3                                                         13           A      22                                                        14           5-1    20                                                        15           5-2    34                                                        16           5-3    24                                                        17           5-4    15                                                        18           5-5    5                                                         19           A      16                                                        20           1-1    49                                                        21           1-4    7                                                         22           6-C    0.2                                                       23           6-1    1                                                         24           6-2    1                                                         25           6-3    52                                                        26           A      17                                                        27           1-3    9                                                         28           1-2    15                                                        29           1-1    62                                                        30           C      2                                                         31           7-1    6                                                         32           7-2    1                                                         33           7-3    2                                                         34           8-1    11                                                        35           8-2    22                                                        36           8-3    40                                                        37           8-4    35                                                        38           8-5    37                                                        39           8-6    6                                                         40           8-1    11                                                        41           9      54                                                        42           1-4    10                                                        43           10     6                                                         44           11     10                                                        45           1-4    9                                                         46           12     61                                                        47           13-1   8                                                         48           13-2   10                                                        49           14-1   0.2                                                       50           14-2   0.1                                                       51           14-3   25                                                        ______________________________________                                         *disintegrations per minute.                                             

The results in Table III demonstrate that improved substantivity of theglycosaminoglycan to hair is provided by various cationic polymers andglycosaminoglycan combinations. The presence and extent of suchsubstantivity is also effected by the relative proportions of cationicpolymer and glycosaminoglycan and application procedures as well as thetype and amount of surfactants or other optional ingredients provided.In an embodiment where the cationic polymer is applied separately andbefore the glycosaminoglycan, the substantivity of the glycosaminoglycanis substantially enhanced.

EXAMPLE 4 Hair Substantivity Using Electrokinetic Streaming Potential

In this example, the substantivity of glycosaminoglycan to hair isevaluated using the previously described electrokinetic streamingpotential procedures, with the results set forth in Table IV. The testsare conducted using treating solutions described by the designated run,in Step 1 as described previously, and 10⁻⁴ N KNO₃ measuring solution,in Step 3 as described previously, except for the sequential polymerapplications in Test Nos. 3 through 5 where the cationic polymersolution is used as the treating solution (in Step 1) followed by theglycosaminoglycan solution as the measuring solution (in Step 3).

                  TABLE IV                                                        ______________________________________                                        EXAMPLE 4: HAIR SUBSTANTIVITY MEASUREMENTS                                    USING ELECTROKINETIC STREAMING POTENTIAL                                      Test     Run    Zeta Potential (millivolts)                                   No.      No.    0 min.     15 mins.                                                                             60 min.                                     ______________________________________                                        1        --     -35*       -35*   -35*                                        2        D      +11        +6     +3                                          3        1-9    +6         -11    -16                                         4        15     +5         -8     -6                                          5        16     +3         -5     -7                                          6        1-1    +6         +6     +3                                          7        A      -40        -40    -40                                         ______________________________________                                         *Average of values varying between -30 and -40 mV                        

Test No. 2 reveals that Cationic Polymer I, a cationic polyelectrolyte,is adsorbed onto hair, changing its normally negative potential topositive, and that it is strongly retained since the potential remainspositive over an hour's period in contact with a polymer-free solution,of 10⁻⁴ N KNO₃.

Tests Nos. 3 through 5, representing the sequential treatment made,strongly indicate that the negatively charged glycosominoglycans ofhyaluronic acid, heparin and chondroitin sulfate, adsorb onto theCationic Polymer I treated hair since in all three cases they transformthe positive potential of hair so treated with a polycation to anegative potential. In the absence of the polycation, none of thesenegatively charged polyions would be expected to adsorb on thenegatively charged hair, as confirmed by the results of Test No. 7.

Test No. 6, representing the co-treatment mode, provides informationindicating that the glycosaminoglycan is adsorbed onto hair under theconditions of this experiment, i.e. when it is present with a tenfoldexcess of Cationic Polymer I. The latter is expected to be stronglyadsorbed to the hair and convert its charge from negative to positive.When this occurs there will be a strong attraction for the polyanionglycosaminoglycan which, however, being present in lesser amount isinsufficient to again reverse the charge, i.e. from positive tonegative.

EXAMPLES 5-6 Skin Treatment and Substantivity EXAMPLE 5 SkinSubstantivity Using Radiolabelled Glycosaminoglycan

In this example the skin substantivity is measured for various cationicpolymer and glycosaminoglycan combinations, using the previouslydescribed general procedures for radioactive analysis unless otherwiseindicated, with the results as set forth in Table V.

                  TABLE V                                                         ______________________________________                                        EXAMPLE 5: SKIN SUBSTANTIVITY MEASUREMENTS                                    USING RADIOLABELLED GLYCOSAMINOGLYCAN                                                        Skin       Amount of                                           Test    Run    Sample     Glycosaminoglycan (μg)                           No.     No.    (mg)       Provided                                                                              Bound                                       ______________________________________                                        1       A       50        40      0.58                                        2       1-1     50        40      0.79                                        3       1-4     50        40      2.71                                        4       B       50        20      0.20                                        5       2-1     50        20      0.28                                        6       2-2     50        20      0.51                                        7       A      100        80      1.45                                        8       1-2    100        80      2.63                                        9       1-4    100        80      6.17                                        10      1-6    100        80      11.56                                       11      A      100        80      1.15                                        12      1-6    100        80      9.92                                        13      1-7    100        80      17.53                                       14      1-8    100        80      9.71                                        ______________________________________                                    

The results in Table V demonstrate that substantivity of theglycosaminoglycan to skin is provided by various cationic polymer andglycosaminoglycan combinations, with enhanced substantivity provided,depending upon the amount of cationic polymer and glycosaminoglycanused, as well as the relative proportions thereof.

EXAMPLE 6 Skin Substantivity Measurements Using Electron Spectroscopy

In this example skin substantivity is determined using electronspectroscopy and the previously described general procedures unlessotherwise indicated. Substantivity of glycosaminoglycan, the cationicpolymer and combinations thereof using either sequential, in Test No. 4,or simultaneous, in Test No. 5, applications of the combination isevaluated and compared with untreated sample, in Test No. 1, as well aswith sample treated with only the glycosaminoglycan, in Test No. 2, orcationic polymer, in Test No. 3, with the results set forth in TablesVIA and VIB.

                  TABLE VIA                                                       ______________________________________                                        EXAMPLE 6: SKIN SUBSTANTIVITY                                                 MEASUREMENTS USING ELECTRON SPECTROSCOPY                                               Surface Composition (wt. %).sup.a                                    Test  Run                       C--O  N+     N/N+                             No.   No.      C      O    N    Carbon                                                                              Nitrogen                                                                             Ratio                            ______________________________________                                        1     Control  83.8   11.4 3.1  --    --     --                               2     E        82.5   11.8 3.9  10.7  0      NA.sup.c                         3     F.sup.b  --     --   --   19.8  0.4    2.0                              4     17-1     81.2   16.0 1.8  18.9  0.2    5.0                              5     17-2     80.8   18.0 0.5  21.9  0.2    2.9                              ______________________________________                                         .sup.a Excluding trace residues of S, P, Si and F impurities.                 .sup.b Based on skin sample prepared under similar conditions using a 0.1     wt.% aqueous solution of Cationic Polymer I.                                  .sup.c Not applicable, no N+ detected.                                   

The results in Table VIA demonstrate that the cationic polymer andglycosaminoglycan combinations, in contrast to the glycosaminoglycansample, are deposited onto the skin as shown by increase in surfaceoxygen content and decrease in surface nitrogen content, characteristicof polysaccharide deposition. The decrease in the level of quaternarynitrogen provided by the cationic polymer and glycosaminoglycancombinations as compared to the cationic polymer alone, despite verysimilar levels of C--O carbon content, indicates the presence of theglycosaminoglycan, which contains no quaternary nitrogen, along with thecationic polymer containing quaternary nitrogen. The increase in N/N⁺ratio, in comparing the cationic polymer and glycosaminoglycancombinations with the cationic polymer only, provides further indicationof glycosaminoglycan providing increased nitrogen content free ofquaternary nitrogen. Enhanced glycosaminoglycan deposition is providedby the sequential application as compared to the simultaneousapplication, shown by the increase in N/N⁺ ratio indicating the presenceof additional glycosaminoglycan on the surface.

Measurement of various depths of surface deposition are provided inTable VIB using angular resolved electron spectroscopy analysis, withthe results set forth in Table VIB.

                  TABLE VIB                                                       ______________________________________                                        EXAMPLE 6: SKIN SUBSTANTIVITY MEASUREMENTS                                    DEPTH ANALYSIS USING ELECTRON SPECTROSCOPY                                    Test    Run    N/N+ Ratio at θ°.sup.a                            No.     No.    78°(56Å)                                                                       38°(35Å)                                                                  18°(18Å)                         ______________________________________                                        6       17-1   6.2         6.4    7.2                                         7       17-2   3.2         3.3    3.4                                         ______________________________________                                         .sup.a Calculated depth into surface, in angstroms (Å), given for         designated angle, (θ), between sample surface and photoelectron         analyzer acceptance optics.                                              

The results in Table VIB show increased glycosaminoglycan deposition onthe surface, for the sample of sequential application of cationicpolymer followed by glycosaminoglycan, as demonstrated by the increasein N/N⁺ ratio at the designated sampling depths, as compared to theconsistent deposition ratio provided by the sample appliedsimultaneously.

EXAMPLE 7 Compatibility

In this example the compatibility of various cationic polymer andglycosaminoglycan combinations, varying in relative proportions, with orwithout additional surfactant or other ingredients, is analyzed usingthe previously described general procedures unless otherwise indicated,with the results set forth in Tables VIIA and VIIB.

                  TABLE VIIA                                                      ______________________________________                                        EXAMPLE 7: COMPATIBILITY MEASUREMENTS                                         Test       Run      Absorbance                                                No.        No.      Initial After ( ) days                                    ______________________________________                                        1          18-C     0.007   --                                                2          18-1     0.018   0.018(11)                                         3          18-2     0.051   --                                                4          18-3     0.070   0.057(10)                                         5          18-4     0.109   --                                                6          18-5     0.201   0.157(9)                                          7          18-6     0.232   0.224(9)                                          8          18-7     0.482   0.619(9)                                          9          18-8     0.731   0.959(9)                                          10         18-9     1.004   1.061(9)                                          11         18-10    1.137   0.989(9)                                          12         19-C     0.015   0.011(9)                                          13         19-1     0.041   0.035(9)                                          14         19-2     0.069   0.066(9)                                          15         19-3     0.118   0.108(9)                                          16         19-4     0.191   0.214(9)                                          17         19-5     0.416   0.474(9)                                          18         19-6     0.700   0.632(9)                                          19         19-7     --      --                                                20         19-8     1.113   0.729(9)                                          21         19-9     --      --                                                22         19-10    1.198   0.719(9)                                          23         20-1     0.005   --                                                24         20-2     0.021   --                                                25         20-3     0.091   --                                                26         20-4     .sup. 0.023.sup.a                                                                     --                                                27         20-5     .sup. 0.000.sup.a                                                                     --                                                28         19-C     0.011   0.006(1)                                          29         21-1     0.705   0.705(1)                                          30         21-2     1.673   1.670(1)                                          31         21-3     2.152   2.156(1)                                          32         21-4     2.260   2.265(1)                                          33         21-5     2.379   2.376(1)                                          34         21-6     2.455   2.446(1)                                          35         22-C     0.003   -0.005(1)                                         36         22-1     0.096   0.070(1)                                          37         22-2     0.283   0.255(1)                                          38         22-3     0.563   0.549(1)                                          39         22-4     0.713   0.552(1)                                          40         22-5     0.754   0.177(1).sup.b                                    41         22-6     0.991   0.010(1).sup.b                                    42         23-C     0.017   0.020(1)                                          43         23-1     0.038   0.039(1)                                          44         23-2     0.055   0.054(1)                                          45         23-3     0.076   0.074(1)                                          46         23-4     0.084   0.098(1)                                          47         23-5     0.103   0.124(1)                                          48         23-6     0.111   0.146(1)                                          49         23-C'    0.002   0.002(1)                                          50         23-7     0.005   0.005(1)                                          51         23-8     0.015   0.012(1)                                          52         23-9     0.026   0.019(1)                                          53         23-10    0.035   0.029(1)                                          54         23-11    0.049   0.046(1)                                          55         23-12    0.066   0.057(1)                                          56         24-C     0.010   0.012(1)                                          57         24-1     0.458   0.480(1)                                          58         24-2     0.852   0.856(1)                                          59         24-3     1.137   1.142(1)                                          60         24-4     1.347   1,345(1)                                          61         24-5     1.469   1.468(1)                                          62         24-6     1.495   1,503(1)                                          63         24-C'    0.002   0.003(1)                                          64         24-7     0.053   0.032(1)                                          65         24-8     0.113   0.091(1)                                          66         24-9     0.163   0.148(1)                                          67         24-10    0.213   0.200(1)                                          68         24-11    0.239   0.219(1)                                          69         24-12    0.255   0.233(1)                                          70         25-C     0.017   0.010(3)                                          71         25-1     0.179   0.199(3)                                          72         25-2     0.445   0.466(3)                                          73         25-3     0.772   0.748(3)                                          74         25-4     0.946   0.936(3)                                          75         25-5     1.146   1.046(3)                                          76         25-C'    0.001   0.000(3)                                          77         25-6     0.018   0.015(3)                                          78         25-7     0.042   0.041(3)                                          79         25-8     0.100   0.086(3)                                          80         25-9     0.149   0.096(3)                                          81         25-10    0.217   0.108(3)                                          82         19-10    0.926   0.861(1)                                          83         33-1     0.921   0.801(1)                                          84         33-2     0.792   0.674(1)                                          85         33-3     0.067   0.098(1)                                          86         20-5     0.214   -0.006(1).sup.a                                   87         33-4     0.304   0.015(1).sup.a                                    88         33-5     0.352   0.011(1).sup.a                                    89         33-6     0.376   0.007(1).sup.a                                    90         34-1     0.173   0.242(1)                                          91         34-2     0.271   0.362(1)                                          92         34-3     0.803   0.747(1)                                          93         34-4     0.225   0.157(1)                                          94         34-5     0.040   0.029(1)                                          95         34-6     0.043   0.033(1)                                          96         34-7     0.169   0.118(1)                                          97         34-8     0.400   0.442(1)                                          98         19-10    1.016   0.891(1)                                          99         35-1     1.062   0.905(1)                                          100        35-2     1.102   0.866(1)                                          101        35-3     0.075   0.073(1)                                          102        20-5     0.298   0.020(1).sup.a                                    103        35-4     0.358   0.000(1).sup.a                                    104        35-5     0.499   -0.003(1).sup.a                                   105        35-6     0.527   0.012(1).sup.a                                    106        34-1     0.218   0.251(1)                                          107        36-1     0.300   0.395(1)                                          108        36-2     1.045   0.941(1)                                          109        36-3     0.217   0.165(1)                                          110        34-5     0.043   0.037(1)                                          111        36-4     0.045   0.026(1)                                          112        36-5     0.217   0.130(1)                                          113        36-6     0.485   0.620(1)                                          114        19-10    0.937   0.854(1)                                          115        37-1     0.958   0.843(1)                                          116        37-2     0.593   0.486(1)                                          117        37-3     0.028   0.030(1)                                          118        20-5     0.235   0.030(1).sup.a                                    119        37-4     0.257   0.008(1).sup.a                                    120        37-5     0.282   0.020(1).sup.a                                    121        37-6     0.229   0.016(1).sup.a                                    122        34-1     0.231   0.289(1)                                          123        38-1     0.420   0.523(1)                                          124        38-2     0.606   0.462(1)                                          125        38-3     0.025   0.024(1)                                          126        34-5     0.050   0.048(1)                                          127        38-4     0.059   0.035(1)                                          128        38-5     0.171   0.135(1)                                          129        38-6     0.321   0.375(1)                                          ______________________________________                                         .sup.a visible coacervate                                                     .sup.b visible precipitate                                               

                  TABLE VIIB                                                      ______________________________________                                        EXAMPLE 7: COMPATIBILITY OBSERVATIONS                                         Test   Run      Visual     Ease of                                            No.    No.      Appearance Mixing  Compatibility                              ______________________________________                                        130    26       Opalescent Excellent                                                                             Excellent                                  131    27       Opalescent Excellent                                                                             Excellent                                  132    28       Opalescent Excellent                                                                             Excellent                                  133    29       Precipitate                                                                              Poor    No                                         134    30       Precipitate                                                                              Poor    No                                         135    31       Precipitate                                                                              Poor    No                                         136    32       Precipitate                                                                              Poor    No                                         137    39-1     Coacervate --      Good                                       138    39-2     Coacervate --      Good                                       139    39-3     Coacervate --      Good                                       140    39-4     Coacervate --      Good                                       141    39-5     Clear      --      Excellent                                  142    39-6     Clear      --      Excellent                                  ______________________________________                                    

The results in Tables VIIA and VIIB demonstrate that various cationicpolymer and glycosaminoglycan combinations, generally depending upon therelative weight ratio of cationic polymer to glycosaminoglycan, providecompatible compositions. The degree of compatibility depends upon notonly the type and amount of cationic polymer and glycosaminoglycanprovided, but upon the presence and amount of surfactants and otheroptional ingredients. Particularly desirable compatible combinations areprovided using Cationic Polymers I, II, III and IV in combination withGlycosaminoglycan I, as well as such combinations with Preservative I.

EXAMPLE 8 Rheology

In this example, the shear viscosity and modulus of elasticity aremeasured for various cationic polymer and glycosaminoglycancombinations, using the previously described procedures unless otherwiseindicated, with the results as set forth in Table VIII. In Test Nos. 8through 11 the measured viscosity and elasticity values are comparedwith calculated values which are the sum of the corresponding values ofthe same concentration and type of cationic polymer andglycosaminoglycan measured in separate solutions. Test No. 8 istherefore compared with Test Nos. 3 and 7. Test No. 9 is thereforecompared with Test Nos. 1 and 4. Test No. 10 is therefore compared withTest Nos. 1 and 5. Test No. 11 is therefore compared with Test Nos. 2and 6. The degree of enhanced rheology is presented in the ratio of themeasured value of the cationic polymer and glycosaminoglycan combinationover the calculated value.

                                      TABLE VIII                                  __________________________________________________________________________    EXAMPLE 8: SHEAR VISCOSITY                                                    AND ELASTICITY MODULUS MEASUREMENTS                                                                        Modulus of Elasticity                                      Shear Viscosity (pascals)                                                                        (G.sup.1, pascals) at Various                    Test      at Various Shear Rates (s.sup.-1)                                                                Frequencies (Hz)                                 No.                                                                              Run No.                                                                              0.19                                                                              4.6  46.5 100  5.0 0.5  0.1                                     __________________________________________________________________________    1  18-C   --  --   0.0230                                                                             0.0224                                                                             0.294                                                                             0.0704                                                                             --                                      2  19-C   1.27.sup.b                                                                        0.256                                                                              0.224                                                                              0.209                                                                              1.54                                                                              0.152                                                                              --                                      3  23-C   0.700                                                                             0.517                                                                              --   --   3.35                                                                              0.327                                                                              0.103                                   4  G      --  0.0318                                                                             0.00973                                                                            0.00748                                                                            0.581                                                                             0.155                                                                              --                                      5  H      --  0.0678                                                                             0.0177                                                                             0.0138                                                                             0.876                                                                             0.275                                                                              --                                      6  I      2.02.sup.b                                                                        0.178                                                                              0.0416                                                                             0.0307                                                                             1.59                                                                              0.565                                                                              --                                      7  I'     1.95                                                                              0.248                                                                              0.068.sup.e                                                                        0.052                                                                              2.63                                                                              1.10 0.539                                   8  23-3   45.3                                                                              6.94 1.75.sup.e                                                                         1.28 39.8                                                                              14.3 7.06                                       (Calculated)                                                                         2.65                                                                              0.765                                                                              --   --   5.98                                                                              1.427                                                                              0.642                                      Ratio.sup.a                                                                          17.1                                                                              9.1  --   --   6.6 10.0 11.0                                    9  18-2   2.41.sup.b                                                                        0.239                                                                              0.0785                                                                             0.0589                                                                             1.24                                                                              0.451                                                                              0.105.sup.f                                (Calculated)                                                                         --  --   0.003                                                                              0.0299                                                                             0.875                                                                             0.2245                                                                             --                                         Ratio.sup.a                                                                          --  --   2.39 1.97 1.42                                                                              2.0  --                                      10 18-4   6.99.sup.b                                                                        0.716                                                                              0.141                                                                              0.097                                                                              2.35                                                                              0.852                                                                              0.200.sup.f                                (Calculated)                                                                         --  --   0.0407                                                                             0.0362                                                                             1.17                                                                              0.3454                                                                             --                                         Ratio.sup.a                                                                          --  --   3.46 1.97 2.0 2.47 --                                      11 19-5   33.1.sup.b                                                                        3.08 0.763                                                                              0.555                                                                              16.2                                                                              6.91 --                                         (Calculated)                                                                         3.29.sup.b                                                                        0.443                                                                              0.2656                                                                             0.2397                                                                             3.13                                                                              0.717                                                                              --                                         Ratio.sup.a                                                                          10.06.sup.b                                                                       6.95 2.87 2.32 5.18                                                                              7.63 --                                      12 40-1   +57%.sup.c                                                                        -26%.sup.c                                                                         +18%.sup.c                                                                         +19%.sup.c                                                                         +79%.sup.c                                                                        +135%.sup.c                                                                        --                                      13 40-2   -34%.sup.c                                                                        -11%.sup.c                                                                         -12%.sup.c                                                                         -11%.sup.c                                                                         -22%.sup.c                                                                        -26%.sup.c                                                                         --                                      14 40-3   77.0                                                                              9.61 1.94.sup.e                                                                         1.36 60.3                                                                              --   20.6                                    15 40-4   -87%.sup.d                                                                        -63%.sup.d                                                                         -16%.sup.d                                                                         -2%.sup.d                                                                          -60%.sup.d                                                                        --   -94%.sup.d                              16 40-5   13.0                                                                              1.13 0.440.sup.e                                                                        0.349                                                                              19.7                                                                              --   9.57                                    17 40-6   +30%.sup.d                                                                        +309%.sup.d                                                                        +367%.sup.d                                                                        +367%.sup.d                                                                        +83%.sup.d                                                                        --   -69%.sup.d                              18 40-7   60.0                                                                              7.87 1.66.sup.e                                                                         0.95 43.9                                                                              20.0 9.90                                    19 40-8   75.3                                                                              8.43 1.74.sup.e                                                                         0.95 48.7                                                                              25.3 14.4                                    20 40-9   77.0                                                                              9.61 1.94.sup.e                                                                         1.36 60.3                                                                              --   20.6                                    __________________________________________________________________________     .sup.a Ratio of measured valve over calculated value.                         .sup.b Based on 0.05 s.sup.-1 shear rate.                                     .sup.c Percent change from measurements of samples without preservative.      .sup.d Percent change from measurements of samples without surfactant.        .sup.e Based on 46.2 s.sup.-1 shear rate.                                     .sup.f Based on 0.01 Hz.                                                 

The results in Table VIII demonstrate that cationic polymer andglycosaminoglycan combinations generally provide a substantialenhancement in both viscosity and elasticity beyond that which would bepredicted through the sum of the viscosity or elasticity values of thecationic polymer and glycosaminoglycan independently. This synergisticenhancement is provided for a wide variety of cationic polymer andglycosaminoglycan combinations, and over a range of relative weightratios thereof, as well as in combination with select surfactants andother optional ingredients. In one embodiment, a maximum increase inshear viscosity enhancement is provided over a range of from about 25:1to about 35:1 of cationic polymer to glycosaminoglycan. In anotherembodiment, the greatest enhancement in elasticity is provided atrelative weight ratios of less than about 25:1 of cationic polymer toglycosaminoglycan.

EXAMPLE 9 Stability

In this Example the storage stability and freeze-thaw stability ofvarious cationic polymer and glycosaminoglycan combinations areevaluated, using the previously described general procedures unlessotherwise indicated, with the results set forth in Table IX.

                                      TABLE IX                                    __________________________________________________________________________    EXAMPLE 9: STABILITY MEASUREMENTS                                                                       Modulus of                                                                    Elasticity                                                                           Storage                                                      Shear Viscosity                                                                         at 5.0 Hz in                                                                         Conditions                                   Test                                                                             Run   Absorbance,                                                                          at 0.19 s.sup.-1 in                                                                     pascals or %                                                                         Time,                                                                             Tempera-                                 No.                                                                              No.   % change                                                                             pascals or % change                                                                     change days                                                                              ture, °C.                         __________________________________________________________________________    1  40-3  -5%    -14.8%    +6.5%   8  20°-25°                    2  40-3  +41%   -35.2%    -25.9%  8  50°                               3  19-5  +36%   -60%      -11%   28  4°                                4  40-3  Unchanged                                                                            -4.7%     +9.7%  28  4°                                5  40-4  Unchanged                                                                            +7.9%     +18.9% 28  4°                                6  40-5  Unchanged                                                                            -20%      -16.6% 28  4°                                7  40-3  +32%   -33%      --     43  20°-25°                    8  40-3  +35%   -51%      --     43  50°                               9  40-3  +31%   -10%      --     64  4°                                10 40-3  +95%   -30%      --     120 20°-25°                    11 40-3  Precipitation                                                                        --        --     120 50°                               12 40-3  +53%   -25       --     135 4°                                13 40-3.sup.a                                                                    Before:      72.4      52.8                                                   After:       97.3      60.8                                                   % Change:    +34%      +15%                                                __________________________________________________________________________     .sup.a Freezethaw analysis based on measurements taken before and after       treatment.                                                               

The results in Table IX demonstrate that various cationic polymer andglycosaminoglycan combinations, particularly in the presence ofpreservative, remain stable and compatible compositions, depending uponstorage temperature and duration. The presence and amount of surfactantor other optional ingredients can also effect the degree of stability.

We claim:
 1. A combination comprising:(1) glycosaminoglycan; and (2)cationic polymer selected from the group consisting water-soluble ofcationic derivatives of cellulose ethers, galactomannan, homo- andcopolymers of ethylenically unsaturated compounds andpoly(N-acylalkyleneimines);which combination provides modification ofthe glycosaminoglycan properties due to the presence of the cationicpolymer.
 2. The combination of claim 1 wherein the glycosaminoglycan ishyaluronan, hylan or other hyaluronan derivative.
 3. The combination ofclaim 2 wherein the glycosaminoglycan is an acid or salt of hyaluronan,hylan or other hyaluronan derivative, a mixture of hyaluronan withproteins and naturally occurring substances derived by the production ofhyaluronan from natural material, or mixtures of such materials.
 4. Thecombination of claim 3 wherein the glycosaminoglycan is an alkali metalor alkaline earth metal salt of hyaluronan, hylan or other hyaluronanderivative.
 5. The combination of claim 1 wherein the cationic polymeris a cellulose ether represented by the overall structural formula:##STR9## wherein: R_(cell) is the residue of an anhydroglucose repeatunit;z is from 50 to about 20,000; and each R₁, R₂ and R₃ isindividually represented by the substituent structural formula:##STR10## wherein: A is an anion; a is an integer of from 1 to about 3;m is an integer of from 0 to about 6; n is an integer greater than orequal to 0, provided that the level of cationic substitution, CS,defined by the average moles of quaternary nitrogen atoms per moleanhydroglucose repeat unit is greater than 0; p is an integer of from 0to about 6; q is 0 or 1; each R₅ and R₇ is individually ethylene, apropylene or a hydroxypropylene; R₆ is a di- or trivalent, cyclic,branched or straight chain, saturated or unsaturated hydrocarbon havingfrom 2 to about 6 carbon atoms, provided there are at least 2 carbonatoms between the nitrogen atom and any oxygen atom; R₈ is hydrogen,hydroxyl, R_(h), alkyl, carboxyl or alkali metal or amine carboxylate,or other terminal group provided that when q is 0 then R₈ is hydrogen oralkyl; each R₉, R₁₀ and R₁₁ is individually R_(h), alkyl, aryl, aralkyl,alkaryl, cycloalkyl, alkoxyaryl or alkoxyalkyl, having at least twocarbon atoms separating the oxygen atom in the alkoxyaryl or alkoxyalkylgroup from the nitrogen atom or together with R₆ forms a heterocyclicring; R_(h) is a hydrophobic group containing an alkyl group having atleast 8 carbon atoms; v is equal to the valence of A; y is 0 or 1,provided that when y is 0 then p and q are 0 and R₈ is hydrogen or otherterminal group.
 6. The combination of claim 5 wherein the celluloseether is polyquaternium-4, polyquaternium-10 or such cellulose etherscontaining hydrophobic groups including polyquaternium-24.
 7. Thecombination of claim 6 wherein the glycosaminoglycan is hyaluronan,hylan or other hyaluronan derivative.
 8. A substantive combination ofclaim 1 wherein the glycosaminoglycan is substantive to keratinousmaterial.
 9. The combination of claim 8 having a relative weight ratioof cationic polymer to glycosaminoglycan which provides an enhanceddegree of glycosaminoglycan substantivity.
 10. The combination of claim9 wherein the relative weight ratio of cationic polymer toglycosaminoglycan provides enhanced glycosaminoglycan substantivity toskin and is greater than about 5:1.
 11. The combination of claim 9wherein the relative weight ratio of cationic polymer toglycosaminoglycan provides enhanced glycosaminoglycan substantivity tohair and is from about 5:1 to about 25:1.
 12. A compatible combinationof claim 1 which provides an aqueous solution substantially free ofprecipitate.
 13. A stable combination of claim 1 which provides anaqueous solution substantially free of precipitation or significantreduction in viscosity over a period of four months at 4° C.
 14. Arheologically modified combination of claim 1 having a viscosity,elasticity or other rheological property of the glycosaminoglycanmodified by the presence of the cationic polymer.
 15. The combination ofclaim 14 wherein the glycosaminoglycan provides enhanced feelproperties.
 16. The combination of claim 1 wherein the relative weightratio of cationic polymer to glycosaminoglycan is from about 0.01:1 toabout 200:1.
 17. The combination of claim 16 wherein the relative weightratio of cationic polymer to glycosaminoglycan is from about 10:1 toabout 50:1.
 18. A hair or skin care composition or combination ofcompositions comprising the glycosaminoglycan and cationic polymercombination of claim 1 in one or more distinct formulations containingsuitable hair or skin care ingredients.
 19. A medical composition orcombination of compositions comprising the glycosaminoglycan andcationic polymer combination of claim 1 in one or more distinctformulations containing suitable medical ingredients.
 20. A combinationcomprising hyaluronan or derivative thereof and water-soluble,quaternary nigrogen-containing cellulose ether represented by theoverall structural formula: ##STR11## wherein: R_(cell) is the residueof an anhydroglucose repeat unit;z is from 50 to about 20,000; and eachR₁, R₂ and R₃ is individually represented by the substituent structuralformula: ##STR12## wherein: A is an anion; a is an integer of from 1 toabout 3; m is an integer of from 0 to about 6; n is an integer greaterthan or equal to 0, provided that the level of cationic substitution,CS, defined by the average moles of quaternary nitrogen atoms per moleanhydroglucose repeat unit is greater than 0; p is an integer of from 0to about 6; q is 0 or 1; each R₅ and R₇ is individually ethylene, apropylene or a hydroxypropylene; R₆ is a di- or trivalent, cyclic,branched or straight chain, saturated or unsaturated hydrocarbon havingfrom 2 to about 6 carbon atoms, provided there are at least 2 carbonatoms between the nitrogen atom and any oxygen atom; R₈ is hydrogen,hydroxyl, R_(h), carboxyl or alkali metal or amine carboxylate, or otherterminal group provided that when q is 0 then R₈ is hydrogen or otherterminal group; each R₉, R₁₀ and R₁₁ is individually R_(h), alkyl, aryl,aralkyl, alkaryl, cycloalkyl, alkoxyaryl or alkoxyalkyl, having at leasttwo carbon atoms separating the oxygen atom in the alkoxyaryl oralkoxyalkyl group from the nitrogen atom or together with R₆ forms aheterocyclic ring; R_(h) is a hydrophobic group containing an alkylgroup having at least 8 carbon atoms; v is equal to the valence of A; yis 0 or 1, provided that when y is 0 then p and q are 0 and R₈ ishydrogen or other terminal group; with the provisos that: (1) the extentof hydrophobic group substitution, HS, defined by the average moles ofsaid hydrophobic groups per mole of anhydroglucose repeat unit, isgreater than 0; or (2) any one of R₉, R₁₀ or R₁₁ taken together with R₆forms a heterocyclic ring and the average value of n per anhydroglucoserepeat unit, is greater than
 0. 21. A process for modifying theproperties of glycosaminoglycan which comprises combiningglycosaminoglycan with an effective amount of cationic polymer.
 22. Theprocess of claim 21 which comprises increasing the substantivity of theglycosaminoglycan to keratinous material.
 23. The process of claim 22which comprises enhancing the feel characteristics provided by theglycosaminoglycan.